H11 E CHENG J CHOW SECOND EDITION CHEMICAL CALCULATIONS AND QUALITATIVE ANALYSISWILSON WELSH PUBLICATIONS LTD. P.O. BOX 70749 KOWLOON CENTRAL HONG KONG © Wilson Welsh Publications Ltd. [All rights reserved. No part of this publication may be translated, reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of Wilson Welsh Publications Ltd. First published April 1977 Second Edition Jan. 1983 Reprinted Jan. 1984 Reprinted Jan. 1985 Reprinted Jan. 1986 By the same authors CHEMISTRY A MODERN VIEW (BK. 1 & 2) (CHEMISTRY A MODERN VIEW EXPERIMENT WORKBOOK (BK. 1 & 2) ‘SYSTEMATIC APPROACH TO CHEMISTRY MULTIPLE CHOICE QUESTIONS Publisher: WILSON WELSH PUBLICATIONS LTD. 70 Fa Yuen Street, 2/F, Mongkok, Kowloon. Tel. 3.300664 Distributor: FAR EAST BOOK COMPANY ‘72 Fa Yuen Street, 4/F, Mongkok, Kowloon, Tel, 3.310285 Typesetter:, _ OCEANSET TYPOGRAPHERS LTD. Printer: MAN YING PRINTING 202-204, Choi Hung Road, 5/F, Block A, Wah Mau Ind’ Bldg ‘San Po Kong, Kowloon, Hong Kong. Tel. 3.217983 3.228772 CHEMICAL CALCULATIONS AND QUALITATIVE ANALYSIS A book of worked examples, problems and basic concepts suitable for ” Revised C.D.C, HKCE, GCE. (O-Level) Chemistry SyllabusesURBAN COUNCIL PUBLIC LIBRARIES Ace. No. 1368793 Class an Aultor cae Icu Preface This book is intended to cover all the aspects of chemical calculations, basic concepts as well as organic and inorganic qualitative analysis required for the present Hong Kong Certificate of Education Examination, the new twoyear course (recommended by Curriculum Development Committee) and for the G.C.E. O-Level. Thus F.3, F.4 and F.5 students may find the book useful Each chapter in this book follows a regular structural pattern. General principles are discussed firs, followed by ample worked examples. The problems at the end of every chapter are all carefully classified and graded, from easy to progressively harder ones. A wide selection of ‘questions taken from recent H.K.C.E.E, and C.D.C. sample papers should prove helpful for learning and revision purposes. In keeping with the modern trend, SI units and terminology are used and mole concept is employed throughout this book. Stock notation is used for naming inorganic compounds and IUPAC system for organic compounds. States of substances are specified in chemical ‘equations where appropriate. In addition, the idea ‘Double Bond Equivalent’ (D.B.E.) is introduced in solving a few organic chemistry problems. There is a tendency in H.K.C.EE. papers to split up questions into several parts so that a candidate who fails to score marks for the final answer may be rewarded for correct intermediate steps. To be in line with this, a number of ‘structured questions’ have been included in most chapters. It is our sincere hope that this new publication will give some contemporary views in elementary chemistry and will provide a valuable guide to students We wish to convey our gratitude to Mr. D. Yu, B. Sc. (Hons) and Dr. D. Ying, Ph. D. (Stanford) for their constant help and advice. April 197 E. Gheng & J. ChowPreface to the Second Edition We are prompted by two motives in revising this book which was first published in 1977. Firstly, the constructive suggestions from many chemistry teachers give us an insight for making alterations and improve- ‘ments. Secondly, there are changes in the content of the HKCE Chemistry Syllabus (which is to be examined for the first time in 1984), and a ‘major feature of this edition is to extend its scope to meet the new requirements. ‘The present book in its second edition has been entirely reset It incorporates a substantial amount of new material, and topics such as ‘metal reactivity series, corrosion, solution patterns, and laboratory techniques and safety have been included, Many more worked examples and questions are added, detailed answers being provided for all questions. It is our pleasure to acknowledge with gratitude the helpful ‘comments received from teachers. We are particularly indebted to Mr. C.K. Lee, BSc. (Hons.), Mr. YH. Lee, BSc. (Hons), Dr. MM. Li, Ph.D., Mr. CH. Lam, BSc. (Hons.), Mr. SK. Lam, BSc. Hons.) and Mr. CN. Tang, BSc. (Hons.). January 1983 E. Cheng & J. ChowCONTENTS CHAPTER PAGE PART A: CHEMICAL CALCULATIONS AND BASIC CONCEPTS 1 ATOMS, MOLECULES & IONS. . . Matt isa collection of minute particles Structure of atoms Relative atomic mass Relative motecular mass and formula mass ‘Molar mass 2 ELECTRONIC CONFIGURATION, PERIODIC TABLE & CHEMICAL BONDING . fi Electronic configuration The Periodic Table Chemical bonding Formulae of compounds 12 3. SHAPES OF SIMPLE MOLECULES & IONS ............... 36 Shapes of simple molecules Representation of 3dimensional structures on paper 4. SIMPLE GAS LAWS . Units used Relationships among P, V and T 5 THE MOLE CONCEPT. .. 4a Counting by weighing Mole concept in general Molar volume Molarity of z solution10 " MASS ANALYSIS OF COMPOUNDS .......... soup Formulae of compounds Composition from formulae Atomic mass from formula Formulae from composition EQUATIONS ‘What an equation is Information from an equation Important points to be noted concerning an equation Ionic equations Finding equation from experiment Balancing equations by inspection Mass and volume from equation VOLUME ANALYSIS IN GASEOUS REACTIONS. ore 105) Gay Lussac’s Law and Avogadro's Law Composition of gaseous mixtures Molecular mass and gas density Molecular formulae from gas analysis METAL REACTIVITY SERIES. ee 2) Metal Reactivity Series Reactivity of metals towards air, water and acid Displacement reactions of metals in aqueous solutions ‘Thermal stability of compounds of metals Reduction of metal oxides Extraction of metals REDOX. . Redox reactions Oxidation number ‘Common oxidizing agents ‘Common reducing agents Balancing redox equations 140 ELECTROCHEMICAL SERIES & ITS APPLICATIONS. ....... 156 Electrochemical Series Electrolysis Quantity of electricity A Faraday as one mole of electrons Rusting of iron 12 1B 4 1s 16 7 VOLUMETRIC ANALYSIS . Titrations in general Detection of end point in acid — alkali (carbonate) titrations Concentration of solution Calculations in titration PERIODICITY & GROUP TRENDS... Periodic Table and periodicity Periodicity of some atomic properties Periodicity of some physical properties Variation in chemical properties across Period 3 Group trends HEAT OF REACTION & BOND ENERGY Exothermic and endothermic reactions Heat of reaction. Bond energy RATE OF REACTION & EQUILIBRIUM Rate of reaction Graphical representation of reaction rate Factors affecting rate of reaction Equilibrium Le Chatelier’s Principle Effects of various factors on equilibrium SOLUTION PATTERNS & SOLUBILITY Polarity of molecules Intermolecular forces Solution patterns and solubility NAMING OF ORGANIC COMPOUNDS ... . TUPAC system of naming 195 m2 238 247 am 283PART B: QUALITATIVE ANALYSIS AND BACKGROUND KNOWLEDGE 18 LABORATORY TECHNIQUES & SAFETY. .... Mixing substances in test tubes Heating techniques Collecting gases Dissolving gases in water Use of pipette and burette in volumetric work Safety in laboratory 19 QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS. . . . Finding molecular structure of an organic compound Concept of Double Bond Equivalent (D.B.E.) ‘Study of chemical behaviour to find functional groups ‘Summary of some important observations and corresponding inferences Polymerization 20 QUALITATIVE ANALYSIS OF INORGANIC COMPOUNDS. . . Qualitative analysis of inorganic compounds Preliminary tests of substance Tests for anions Tests for cations ‘Answers to Exercises The Periodic Table Colours of Common Inorganic Compounds Approximate Atomic Masses & Physical Constants ‘Questions at the end of each chapter 300 327 374 41s 453 456 ART A 1 ATOMS, MOLECULES & IONS MATTER IS A COLLECTION OF MINUTE PARTICLES Matefials found in nature are in general not pure; they are mixtures. Most of the substances found in a chemical laboratory are pure substances. Pure subsiance can cither be a compound or an element. The simplest substances are called elements, which cannot be decomposed into simpler types of matter by physical or chemical changes. Pure substances that contain more than one clement are called compounds, which can be decomposed by energy into simpler substances. AAI matter is made up of three types of particles: atoms, molecules and ions. ‘An atom is the smallest particle of an element that can take part in a chemical change. ‘A mdecule is the smallest particle of an element or compound which can exist in a free and separate state ‘An ion is an atom or group of atoms possessing an electrical charge. Atomicity of an element is the number of atoms in one molecule of the element. Atomicity Examples 1 noble gases (He, Ne, Ar, Kr, Xe, Ra) 2 most gases (Na, On, Cla, Ha ete.) 3 ozone (Os) 4 yellow phosphorus (Ps) 8 rhombic sulphur Ss) indefinite solid metals carbon (i the form of diamond or raphe) ete,STRUCTURE OF ATOMS An atom consists essentially of a minute, extremely dense central nucleus surrounded by negatively charged particles called electrons. The nucleus is composed mainly of protons and neutrons (the only exception being hydrogen which has no neutron; see Example 1.1). Proton, electron and neutron are collectively known as the three fundamental particles ofan atom. ‘A diagrammatic representation of an atom is shown below: (nucleus) consisting of ‘roton(s) and mewron(s \ The table below gives the relative charges and masses of the three fundamental particles. clectron(s) move around nucleus Fundamental Relative | Mass particle Symbol | charge | (in Yam) Electron core | 1-v | 0.00055 Proton P 1+ve | 1.0075 Neutron a ail 1.009 ‘The number of protons in the nucleus determines the identity of aan element. This number is called the ATOMIC NUMBER (Z).. In a neutral atom, the number of electrons around the nucleus is equal to the number of protons in the nucleus. No. of protons = no, of electrons = atomic number (fora neutral atom) If an atom or group of atoms gains or loses electron(s), an electrically charged particle called ion will be formed. For example, a chlorine atom C1 gains 1 electron to give a CI"ion;a magnesium atom Mg loses 2 electrons to form a Mg” ion * The meaning of a.m. will be piven on ps. [As the mass of an electron is negligibly small when compared with that of @ proton or neutron, the mass of an atom is approximately equal to the sum of the masses of protons and neutrons in the nucleus. ‘The MASS NUMBER(A) of an atom is defined as the sum of the ‘number of protons and neutrons present in the atom, ISOTOPES are different atoms of the same element; they have different numbers of neutrons and therefore different masses (mass numbers). Isotopes of an element have the same chemical properties because they hhave the same number and arrangement of electrons. (Arrangement of electrons will be discussed in Chapter 2.) To specify particular isotope of an clement, it is useful to write the full atomic symbol of the atom, the general form of which being shown below: ‘mass number A Atomic Symbol atomic number -* Z For example, the three isotopes of hydrogen are represented as ‘ H(protium), 7H(¢euterium) and ? (tritium). ‘Example 1.1 Find the ruinber of protons, electrons and neutrons in each of the {following atoms: (a) \H (b) 38C1. (@) No.of protons = 1 = no. of electrons No. of protons + no. of neutrons = mass no. = no. of neutrons = 1 —1=0 (©) No. of protons = 17 = no, of electrons No. of protons + no. of neutrons = mass no. :. no, of neutrons = 35 ~ 17 = 18 Example 1.2 Find the number of electrons in (a) an iodide ion ” (0) an aluminium ion AP*. (Atomic numbers of iodine and aluminium are 53 and 13 respectively.) (@) Inn iodine atom, no. of electrons = no, of protons atomic no. of iodine = 53,Since an iodide ion carries 1 negative charge, it has 1 electron more than that of an iodine atom, ie. it has 53+ 1 = 54 electrons, (©) In an aluminium atom, no. of electrons = no. of protons atomic no. of aluminium = 13, Since an aluminium ion carries 3 positive charges, it has 3 electrons les than that of an aluminium atom, ie. it has 13 — 3 = 10 electrons. Example 1.3 Refer tothe table below and answer the questions which follow: vate | Atomic | Mass ‘Number of oa number | number | protons | neutrons | electrons ep | 24 2 | oa a | 2% 30 | 23 R sa | 26 4 s 36 ome anzs (P, Q R, S are not atomic symbols of elements.) (a) Calculate the missing numbers in the table. (b) Calculate the charges (if any) on the particles. Which of the particles are ions? (c) Which of the particles represent the same element? Which particles are isotopic with each other? Explain your reasoning. (@) Particle P Number of protons = atomic number = 24 ‘Mass no. = no. of protons + no. of neutrons = 24428 = 52 Particle Q With similar reasoning as shown above, number of protons = 26; mass number = 26 + 30= 56 Particle R Atomic number = number of protons = 26 No. of neutrons = mass no. ~ no. of protons = 54 ~26= 28 Particle $ No. of protons = mass no. ~ no. of neutrons 6 30 = 26, ‘Atomic number = number of protons = 26 (b) Since particle P has 24 protons and only 21 electrons, it carries 24 ~21 =3 positive charges. Similerly, ‘charge on Q = 26 ~ 23 = 3 positive charges; charge on R = 26 ~ 24 = 2 positive charges. Since $ has an equal number of protons and electrons, it is a neutral atom. ‘Therefore P, Q and R are ions. (©) @Q Rand $ represent the same element since they have the same number of protons. R is isotopic with Q (R and Q have same no. of protons but different no. of neutrons); is also isotopic with S (R and 'S have same no. of protons but different no, of neutrons); but S is not isotopic with Q (S and Q have same no. of protons and same no. of neutrons). S and Q ate different — Sis a neutral atom of an element while Q is an ion of the same element carrying 3 positive charges RELATIVE ATOMIC MASS ‘Atoms are so very minute that in stating their masses, units such as kg or g are inconvenient. For example, a 'H atom would have a mass of 1.67 X 10* g. For comparing masses of atoms, a reference standard ‘of mass is needed which will give relatively convenient numbers. ‘The standard chosen is '2C, which isan isotope of carbon containing 6 protons and 6 neutrons. The mass of this particular isotopic carbon atoms taken to be exactly 12 atomic mass units (an... RELATIVE ISOTOPIC MASS _™S of 1 stom ofthe isotope (or ISOTOPIC MASS) Jz % mass of | atom of 7C It can be seen that mass number of an isotope + its isotopic mass. Suppose an element consists of say, 4 isotopes, then there would be 4 different isotopic masses, one for each of the isotopes. However, for the element concerned, there is still only J atomic mass. Hence the atomic mass of an element is determined by two factors: the isotopic‘masses of the isotopes present in the element and their relative proportions (@bundance) in nature The relative atomic mass (A,) of an clement is thus the weighted ‘average of the isotopic masses on the '2C = 12.00 scale. RELATIVE ATOMIC MASS (or ATOMIC _ 2Vetage mass of 1 atom of the element MASS) of an - Fz X mass of 1 atom of Pc element (A,) 2 On the '2C = 12.00 scale, the mass of a proton or neutron is not exactly one unit. Also, most elements are mixtures of isotopes, so accurate atomic masses are never whole numbers. However, for most purposes in elementary chemistry, approximate atomic masses are used (se p.436), which are often taken to be whole numbers. Note: Values of relative atomic masses are usually written in the form such as Na = 23, which is the shorthand for ‘the relative atomic ‘mass of sodium is 23°, Example 1.4 Natural silicon consists of a mixture of three isotopes and its atomic umber is 14, Jsotope Isotopic mass $ abundance by no. of atoms A 28.0 92.2 B 29.0 47 c - 30.0 BL (a) In each of the three isotopes, how many protons and neutrons are there in each atom? (b) Calculate the atomic mass of silicon. @ In general, for a particular isotope, mass no. + isotopic mass. For isotope A, mass no. = no. of protons + no. of neutrons = 28, Since no. of protons = 14, no. of neutrons = 28 — 14 = 14 ive. there are 14 p and 14 n in each atom of A. Similarly, there are 14 p and 15 n in each atom of B; there are 14 p and 16 n in each atom of C. (©) Atomic mass _ weighted average of the isotopic masses of ofsilicon —~ the isotopes present = 28.1 RELATIVE MOLECULAR MASS AND FORMULA MASS Many elements and compounds consist of molecules. The relative ‘molecular mass of a substance is defined as follows: RELATIVE MOLECULAR substance MASS (or avenge mim of | oleae ofthe MOLECULAR “1X mass of 1 atom of 13 MASS) of a 2 substance (M,) Example 15 Find the molecular masses of the following compounds: (a) Cl (0) Calls ,0¢ coon. (@) Mp= 12+1X4=16 Cn (b) Mp = 12% 6 +1 X'12 + 16 X 6 = 180 Many substances do not have discrete (separate) molecules, e.g, solid ‘metals, salts, alkalis. For these, we introduce the term formula mass. FORMULA MASS = the sum of the atomic masses of the atoms present in the formula representing the element ‘or compound. The concept of formula mass is not limited to elements or compounds only. It is also applicable to ions, electrons as well as nuclear particles, or other specified groups of particles. Example 1.6 Find the formula masses of the following (a) NaOH (6) NHgFe(SOs)2.12H;0 —(c) SOP 3 +16+1=40 44+1X 4456+ (2+ 16X 4) 2 + 12x (1X 2+ 16)= 482 (@) Formula mass (b) Formula mass(©) Formula mass = 32+ 16x 4= 96 (Note: Formula mass of an ion is calculated in the usual way because ‘mass of electrons is negligible.) MOLAR MASS The isotopic mass, atomic mass, molecular mass and formula mass defined above are all ratios only (ic. they carry no units.) For calculations in chemistry, the following terms have to be introduced. ‘One MOLE of a substance is the amount corresponding to the formula ‘mass in gram unit. Thus 1 mole of H2S would correspond to 34 g of HaS and 2 moles of H,S to 68 g of HS and so on. (A more detailed explanation of the mole concept is given in Chapter 5.) ‘The MOLAR MASS of a substance is the mass in grams of one mole of it. Thus the molar mass of HS is 34g. It follows that: Mass of a _ no. of moles of ,, molar mass of substance “ the substance ™ the substance Example 1.7 (a) What is the mass of 0.15 mole of NaOH? (b) What is the number of moles of CaCOs in 10 g of CaCOy? (e) What is the number of moles of Na” ions in 35.5 @ of NaxSOx? (@) Mass 10. of moles X molar mass = 0.15 X (23 + 16 + 1)=6.0g mass in ‘molar mass of CaCO; oa W+i2+16x3 (©) No. of moles of CaCO, = 0.10 (©) No. of moles of NazSOx = 5535 Since 1 mole of Na,SO, gives 2 moles of Na* ions, umber of moles of Na* fons = 0.250 X 2 = 0.500 Example 1.8 The mucleus of fluorine atom has a radius of 5.00 X 10°? cm and a mass of 3.15 X 1079 g. Calculate the density of the fluorine nucleus, assuming that itis spherical Volume of the nucleus =4 m1? = 4x 3.14 X (6.00 x 10} em? = 5:23 X 1027 em? mass _ 3.15 X 10° volume ~ 5.23 1057 = 6.02 X 10" gem” Density = Note: The density of fluorine nucleus is incredibly high when compared y 2 3) with that of fluorine gas, which is only 1.7 X 10° g cm” at 1 atmospheric pressure and 0°C. This shows that fluorine nucleus is extremely dense. exercise 1 ~1~** Find the number of protons, electrons and neutrons in each of following atoms: (@) 13N Oo Ba © RU @*U What isthe relationship between ®2*U and *25U2 What is the effect of changing the number of (@) protons (6) electrons of a particular atom? (©) neutrons Complete the following table: Atomic | Mass Number of Particle | number | number | protons | neutrons [electrons @ 'Hatom 1 () ?Hatom (©) *Hatom @ 2H ion (©) Hion 1 ( "C atom 6 @) °C atom (h) Non 14 7 i) Neatom 10 10 @)_ Mg?" ion 26 10 (&) $? ion 16 18 For (h), @, G) and (K), give the full atomic symbols for the isotopes concerned.4) Natural chlorine consists mainly of a mixture of 2 isotopes: ; Relative Symbol Isotopic mast, pay ial 350 154 Ha x10 246 Calculate the atomic mass and molecular mass of chlorine. 5) Naturally occurring bromine (atomic mass = 79.9) consists of a mixture of two isotopes: ”°Br and ** Br. Calculate the percentage abundance of the two isotopes in natural bromine. 6) The mass spectrometer trace shown was obtained for an element E: Calculate the atomic mass of B. Detector current 6 reading. Se 2s 7 pr 20 29 eso eee 77g ae (Note: Mass spectrometer is an instrument which can be used to determine atomic masses and molecular masses. The relative abundance of the isotopes is found from the relative ‘magnitudes of the electric currents produced in the detector.) 7) Using the list of relative atomic masses on p.456, find the formula mass of each of the following: (2) Cols (b) CH;CHO (©) NaCl (@) FeSO, .7H,0 (@) Ks [Fe(CN).] (f) Nat (®) Nos () [AI(OH), > 8) For the species given in question (7), find the mass of 0.100 mole ofeach 10 9) Find the rrolar mass of (a) (COOH): .2H0 (b) NaxCOs, What is the essential difference between the molar mass and formula mass of a substance? 10) How many moles of compound are there in (®) 50 g0fH,0 (b) 28g of KOH (©) 20.0 gof CuS0,..5H:0 (@) 30.0 g of Ks [Fe(CN)e]? 11) Find number of moles of K" ions in (@) 28 g0f KOH (©) 30.0 g of Ks [Fe(CN).]- 12) 0.25 mole of a certain compound corresponds to 11g. What is the ‘molar mass of the compound? uELECTRONIC CONFIGU- RATION, PERIODIC TABLE & CHEMICAL BONDING ig the central minute nucleus. These shells are at different. distances from Ye nucleus and are numbered as Ist, 2nd, 3rd, 4th, .. (or K, L, M,N, \..) outwards from the nucleus. Each shell can only 4h (Ny shell 3rd (shell ‘2nd(L) shell Ist (K) shell ‘The way of distribution of electron in various shells is called electronic configuration (or electronic arrangement or electronic structure). To find the electronic configuration of the atom of a particular element, the number of electrons present is found first and then they are ‘fed’ into the shells successively, starting from the shell nearest the nucleus (Le. the 1st shell ). When a particular shell is ‘full’, any extra electrons are fed {nto the next outer shell and so on until all are accomodated. By observing these rules, the electronic configurations of the twenty simplest atoms (hydrogen to calcium) can be found. These are shown in the following table. R jc | No. of electrons Atomic | Electronic Atom | Symbot in electron shells be | Configuration Hydrogen | H feel 1 Helium =| He 2 |2 2 Lithium | Li 3 |2 1 21 Beryllium | Be 4 |2 2 2,2 Boron B s |2 3 2,3 Carbon | C laze 4) 244 Nitrogen | N 712 5 2.5 Oxygen | O 26 2,6 Fluorine | F 9 |2 7 247 ‘Neon Ne so |2 8 2,8 Sodium | Na n /2 8 1 2.81 Magnesium} Mg | 12 |2 8 2 2,8,2 Aluminium] Al IS 2) ee 2,8,3 Silicon Si Moheg 4 2,8,4 Phosphorus) P 1s |2 8 5 2,8,5 Sulphur | $ Gn OG 2,8,6 Chlorine | Cl 7 |2 8 7 2,8,7 ‘Argon Ar w |2 8 8 2.8.8 Potassium | K i |2 8 8 1] 2,881 Calcium | Ca Fy 20 0 ol ain Note that for K and Ca, the actual electronic configurations are not the same as we might predict (Le. 2, 8, 9 for K, 2, 8, 10 for Ca). The explanation is too complicated to be discussed here. Representing electronic configuration by diagram Electronic configuration of an atom can be represented by an electronic diagram (or electron diagram). Usually the nucleus is represented by the symbol for the atom (or just a black dot), electron shells by concentric circles around the nucleus, and electrons by dots or crosses. Electronic diagram of magnesium atom is given below. 13C Mg(2.8:2) : THE PERIODIC TABLE ‘As can be seen from the table of electronic configurations of the 20 simplest atoms, elements with the same outer electronic structure appear at periodic intervals, eg. Li, Na and K atoms all have 1 electron in the outermost shell. To emphasize this periodicity, elements can be arranged in the form of a Periodic Table in which they are arranged in increasing order of atomic numbers (ie. number of protons or number of electrons) ‘They are arranged such that elements with the same number of outer shell electrons occur in the same vertical column or group in the table. Horizontal rows of elements across the table are called periods. If we study electronic configurations of elements given in the table overleaf, the following rules can be drawn for elements in main groups: (@) The number of occupied electron shel (b) The number of outer shell electrons = group number ((e. an element belonging to Group 7 has n electrons in the outermost shell ofits atoms.) To illustrate the above rules, let us consider the element chlorine. The electronic configuration of chlorine atom is 2, 8, 7. Thus the number of ‘occupied electron shells is 3 which is equal to the period number of chlorine; the number of outer shell electrons is 7 which is equal to its group number. In the Periodic Table shown, a zig-zag boundary lin is drawn separating metals from non-metals. However, this division is in fact not definite as a few elements (called sem?metals) have properties resembling both metals and non-metals ‘As a simple rule, metals are elements with 3 or les than 3 electrons fn their outermost shells; non-metals are elements with more than 3 electrons in their outermost shells, (Note that this rule has quite a number of exceptions: H, He and B have 3 or les than 3 electrons in the outermost shell, yet they are non-metals; the elements at the bottom of groups IV, V and VI have more than 3 electrons in the outermost shell, yet they are metals.) = period number Groups ° Vv vi Vu m tectonic configuration transition groups (metals) i main groups “The Periodic Table (party drawn) 1sCHEMICAL BONDING Most substances are composed of an aggregate of atoms or ions held together by electrostatic forces of attraction. For example, copper metal consists of an aggregate of atoms; hydrogen gas Hy consists of molecules each containing 2 atoms; sodium chloride solid consists of an aggregate ‘of positive and negative fons. Chemical bonding (or simply bonding) is a description of the way in which atoms join together (by redistributing their outer shell electrons to produce attractive forces) in making up elements and compounds. The strong electrostatic forces binding the particles together are referred to as chemical bonds (or simply bonds). The exceptional chemical inertness of noble gases indicates that their electronic configurations are very stable. Helium, the first member of the group, has 2 electrons (@ duplet), while all the other group members, hhave ight electrons (an octet) in the outermost shell. Elements other than noble gases tend to attain the electronic configuration of the nearest noble gas by electron redistribution. Those electrons involved in redistribution are called valence electrons. For the first 20 elements, valence electrons are found in the outermost shell. TYPES OF CHEMICAL BOND There are different types of chemical bonds, depending on how electrons are redistributed in their formation: (1) Tonic (or electrovatent) bond (2) Covalent bond ) Intermediate types of bond between ionic and covalent (@) Metallic bond (J) Ionic bond (electrovalent bond) Tonic bonding usually occurs between metals and non-metals. Metals are electropositive (Le. their atoms tend to form positively charged ions by losing one or more electrons) while non-metals are electronegative (ic. their atoms tend to form negatively charged ions by gaining one or more electrons). Therefore when they react, there is electron transfer from metals to non-metals, resulting in the formation ‘of positively charged ions (cations) and negatively charged ions (anions), which have the same electronic configurations as the nearest 16 noble gases. (Sometimes, a group of atoms called radical can also lose or tain electrons to form cations or anions, e.g. SOx", HCOs", NH’, [Cu(t,0).]”", etc.) The oppositely charged ions then cluster around cone another, forming a three-dimensional orderly arrangement called giant ionic ‘lattice. The noneirectional electrostatic force binding the ions together is called ionic bond. Tonic compounds include salts and bases. The following example shows the reaction between a sodium atom, and chlorine atom to form a sodium ion and chloride ion. ko: #2 scton ®) ofNe = Seaton orc i atom latom 8,1 28,7 + 7 tectoa Nation = Crin a aaa ——— octet attained in outermost shell Note: In the above diagrams, the electrons are shown by ‘dots’ and ‘crosses’. By using these symbols, the number of electrons in various shells can be readily counted, and the transfer of electrons easily followed. However, it must be bore in mind ‘that the symbols do not show the actual spatial distribution of electrons, and electrons of different atoms are in fact indistinguishable. 7In sodium chloride crystal, the sodium ions and chloride ions are arranged to form a cubic structure as shown below: wai tA e-N ofc (2) Covalent bond Electron transfer cannot take place between nonsmetals since they are both electronegative. Instead, they would share some of their electrons in order to attain a noble gas configuration. The shared electrons (negatively charged) “sandwiched” between the bonded atoms attract both nuclei (positively charged) by electrostatic attraction. This directional attractive force is called covalent bond. Sharing of 2 electrons (je. 1 electron pair) gives rise to a single covalent bond (tepresented by a single stroke —). Similarly, sharing of 4 electrons gives rise to a double bond (represented by a double stroke =) and 6 electrons to a triple bond (represented by 2 triple Examples of compounds with H H “i I single covalent bonds: H—C—H, H-N-H, H-O—H I H ce eB double covalent bond(s): C=C, 0. 2o™~ Hf triple covalent bond: | N=N, H-C=C—H 18 The following example shows the reaction between carbon and ‘oxygen atoms to form a carbon dioxide molecule. © © ©O= GOO atom —Catom_—Oatom carbon dioxide molecule 26) aay 6) lecuon of C atom lestton of O ators |A shared pair of electrons is called a bond pair. Study the lectronic structure of carbon dioxide molecule. The carbon atom is associated with 4 bond pairs while each of the two oxygen atoms with 2 bond pairs. In addition, each oxygen atom has 2 unshared pairs of electrons in the outermost shell — they are referred to as nnon-bonding pairs or lone pairs. Note that carbon atom has no lone pair in the molecule. Covalent bonds exist not merely in molecular compounds (i. compounds consisting of discrete molecules). They also bind atoms together in a giant covalent structure e.g. diamond, in which every carbon atom is linked by covalent bonds to 4 other atoms. aa carbon atoms tT covalent bonds Structure of diamond 19Giant covalent structures are solids with very high melting points and boiling points. This is because a lot of energy is required to break the many strong covalent bonds in separating atoms during meting or boiling. Dative covalent bond In a normal single covalent bond, each atom contributes one clectron for the shared pair. However, in some compounds, a bond is formed by the sharing of a pair of electrons, both of which originate from the same atom. ‘A dative covalent bond (or coordinate bond) is a covalent bond in which both shared electrons come from one of the bonded atoms. ‘The atom which supplies the electron pair is called the donor atom, while that which receives the electron pair is the acceptor atom. A dative covalent bond is indicated by an arrow pointing from donor atom to acceptor atom, Let us look at the following example: a Hrox + Ht water Ihydrogen —_hydroxonium ion molecule ion oo aoy 1 1 H-Of + HO Fe Note that all the 3 O-H bonds in HO" are in fact identical — dative ‘and normal covalent bonds differ only in the way they are formed. Wecan aswell eproventtheion as [4] n-9-u (3) Intermediate types of bond In many cases when a chemical bond is formed, neither is the transfer of electrons complete nor the sharing of electrons equal. ‘Therefore, the purely ionic bond and purely covalent bond are only two extremes in the bonding situation: there are many intermediate types ie. bonds can be partially ionic and partially covalent in character. Take the example of hydrogen chloride H — Cl. Its bonding is basically covalent, but the chlorine atom attracts the shared pair of electrons more than hydrogen does; this gives rise to a partial positive charge on hydrogen and a partial negative charge on chlorine, leading to a small percentage of ionic character in the molecule. Thus hhydrogen chloride molecule is an electric dipole (having 2 opposite electric poles) and can be represented as °*H — Cl”. Such a molecule is described as polar, Other polar molecules include water and Comparison of ionic and molecular compounds Tonic compounds ‘Molecular compounds Examples _| NaCl, KMnOs,KOH,MgO_| CHs,NHs, Hz0, CCle Constituent | Tons Discrete molecules particles Attractive | Strong ionic bonds bind | Strong covalent bonds forces ions together throughout | bind atoms together resent the crystal lattice within a molecule. Separate molecules are attracted only by weak intermolecular forces (e.g. van der Waals’ forces) Usual High melting solids, asa | Gases, low-boiling physical | lot of energy is required | (volatile) liquids or low: states | to break strong ionic bonds | melting solids, as it is in separating ions quite easy to overcome the weak intermolecular forces in separating molecules ‘Solubility | Generally soluble in polar | Generally insoluble in solvents (e.g. water) and | water unless they react insoluble in non-polar _| with it (eg. hydrogen solvents (e.g tetrachloro- | chloride reacts with methane CCly) water to give hydro: chloric acid); generally soluble in non-polar solvents "*Sce Chapter 16 for further details. 21Tonic compounds ‘Molecular compounds Electrical | Non-conductors in solid | Non-conductors because conductivity | state because ions are there are no ions at all; not mobile;conduction _| aqueous solutions may takes place when ions conduct electricity if become mobile in molecules react to form ‘molten state or in ions (eg. hydrogen aqueous solution, but is | chloride reacts with accompanied by water to give decomposition hydrochloric acid | HOG) + H,0(@) + Hs0"(aq) + CV(aq)) (4) Metallic bond ‘Atoms in metals are packed closely together in an orderly way. Each atom contributes its valence electrons to the common pool of electrons (called delocalized electrons) which move freely throughout the whole giant metallic structure. The contribution of one or more delocalized electrons by each atom leaves a positively charged ion. (For example, in aluminium metal, each atom contributes 3 delocalized electrons, leaving an ion carrying 3 positive charges.) Thus a simple model of metallic structure is that of a ‘sea’ of electrons around a giant structure of metal ions. "ea of delocalized electrons posiinely charged fons Se of delocalized Simple mode of metalic structure ‘The electrostatic attraction between delocalized electrons and positive {ons is called metallic bond. ‘The presence of delocalized electrons accounts for high thermal and electrical conductivities of metals. 2 Example 2.1 The following table gives information about the properties of several substances. ‘Substance | Melting | Boiting | Electrical conductivity point (°C) | point (°C) | Solid [ Liquid A 39 357 | good | good B 80 218 | none | none c 147 1387 | none | good D 68 ~67 | mone | none E 1610 2230 | none | none F 98 890 | good | good Answer the following questions (Give your reasoning in each case.) (a) Which of them is gaseous at room conditions (25°C and I atmospheric pressure)? (b) Which of them isa liquid at room conditions? (6) Which of them are metals? (@) Which of them is an ionic compound? (¢) Whichof them are molecular compounds? (£) Which of them has a giant covalent structure? (g) Predict the solubility behaviour of substance Cin (i) water (ii) tetrachloromethane CC (h) Given that substance B is insoluble in water, while D readily dissolves in water 10 give a solution with high electrical conductivity, how ‘can you explain the difference? (@) Substance D, since its boiling point is well below room temperature. (©) Substance A, since its boiling point is higher than room temperature ‘while its melting point is lower than room temperature. (©) Substances A and F, since they are good electrical conductors in both solid and liquid states (@) Substance C, since it is a non- 3 outemest shell (for non-metals) oe \ MgCl, and C0, refer o _ ote nono electronic diagrams shown | [Mal** 2[ C1: J” MaCls covalent using the oe Mg™ 28 Cl 288 simple re: tonic covalent ok imeal + non-metal rcxBx co, oni bonding : ton-metl + non-metal covalent bonding 4, Write the empirical Example 23 formu of compound The atomic munbers of fv elements A, B,C, Dan E are given Blow showing only the MgCl, CO, (A, B, C, D and E are not atomic symbols.) simplest integral ratio 1 ——__—— of aumbe of ‘loment_[ Atomic amber onrtventpatces 5S. Write the structural | B 6 formula of compound MgCl) c 8 to show also the bonds : D 17 present z 2 6. Using information 2+, (a) State, with reasons, which of these elements exist as diatomic molecules from (1), convert the at room conditions. Draw electronic diagrams of the molecules. structure formula OVO Oo (b) Which of the elements has the greatest tendency to form cations? int electronic Wash diagram using ‘dots’ Mer 2.8 Cr 2.8.8 iy’ and ‘crosses’ to. ’ (c) Give electronic formulae for the following compounds. Name the type represent electrons Key: x=electron | Key: *=electron of bonding in each case. ‘of Mg atom of O atom (i) Compound formed between A and C + = electron + =electron (ii) Compound formed between A and D of atom of C atom (iti) Compound formed between B and C. 2(d) Which compound mentioned in (c) would have the lowest melting point and boiling point? Why? (e) Would you expect element E to form any compound at all? Why? (@) Firstly, the electronic configurations of the elements are deduced from their atomic numbers: Element Atomic number Electronic configuration A 3 21 B 6 2.4 c 8 26 D a 2,8,7 E 18 2,8,8 Element A, having only 1 electron in the outermost shell of its atoms, should be a metal and therefore does not consist of molecules at all. Element B, having 4 electrons in the outermost shell of its atoms, cannot attain a noble gas configuration by forming @ diatomic ‘molecule. Element £ has already a noble gas configuration and therefore its atoms have no tendency to join up. Each of elements and D can attain a noble gas configuration by forming diatomic molecules. Co O© (©) A, since it is a metal (clectropositive in nature) while all others are non-metals. © @LAT (EE LAT" ionic @ LAY 02 T° ionic Gil) REE B:Ae covalent 28 (a) Compound BC; would have the lowest melting point and boiling point, It is a molecular compound. Only weak intermolecular forces (wan der Waals’ forces) of attraction exist among the discrete molecules, to little energy is required to overcome these forees during melting and boiling. (¢) No. E (with electronic configuration of 2, 8, 8) is a noble gas, The ‘octet is already complete, so F shows no chemical reactivity. Example 2.4 ‘The formula of an ionic compound is found 10 be XY (X is ametal while Y is a non-metal; X and ¥ are not atomic symbols). Both ions have the electronic configuration of 2, 8. (a) What is che tonic charge on X? (6) What is the ionic charge on Y? (c) What are the electronic configurations of atoms of X and Y? (d) Identify elements X and Y and write the structural formula for the compound XY. (a) and (b) Refer to Step 3 in Example 2.2: ‘onic charge on onchange on % 2 2 + (positive charge since X is a metal) — (negative charge since Y is a non-metal) Tonic charge on. Ionic charge on (©) X atom has 2 more electrons than X** ion, hence its electronic ‘configuration is 2, 8, 2; Y atom has 3 less electrons than ¥°~ ion, hence its electronic configuration is 2,5. (@) Xis magnesium, ¥ is nitrogen. Son ‘The structural formula of the compound is (Mg*)s(N?")a 29Example 2.5 (b) Classify them into metals and non-metal. Refer to the compound ammonium chloride NHC (©) What will be the predominant type of bonding for the compound ; formed between (a) Write its electronic formula, (b) State the types of bonds present in this compound. @ AandB (i) Band (ii) A and D? {c) Is ammonium chloride @ molecular compound or ionic compound? (@) Would you expect @ compound to be formed between A and £7 Explain, © H * i (@)_ Which element(s) consists) of. @ diatomic (i) monatomic molecules at room conditions? 3) (a) An atom X has mass number 39 and contains 20 neutrons. To ‘what group of the Periodic Table does it belong? (b) X forms a compound X,Y. Suggest an clement that ¥ might (2) Toni bond exists between Nii” and CI-ions; covalent bonds hold N Posed crea fey choie and 4 H atoms together within the NH," ion. (© 111s an tonic compound (though there ae covalent bonds within the 4) €4) Complete th fellowing tl ee ) (a) Complete the following table: ‘ Fremont |4t0mte [Mas] No.of | No. of No.of | Hlecronic ‘emen | number| no. | protons | neutrons| electrons | configuration EXERCISE 2 x 120 |24 1) The electronic configurations of s le its bel z 6 6 = ome elements are gine below: a ea [aa HU) He) AN, 8,3)__PQ,8,5) : ” ‘Sr(2, 8, 18, 8, 2) At(2, 8, 18, 32, 18,7) . (b) (i) Name X, Yand Z. (@) As far as possible, try to classify them into either metals or non- (2) What ie the structural formula af the compound formed ital between X and 2? (©) To what () group (i) period in the Periodic Table does each of Ca red eae NSN TN) them belong? 2) The following table gives some information about the elements A, 5) The number of protons, neutrons and electrons in particles A — F are B,C, Dandé. given in the following table: Flement Atom number Particle | Proton | Newton | Bleciron A 1 A 3 4 2 2 5 a 3 10 10 c 2 ¢ 2 R 2 > 6 > 0 8 0 E 18 £ 0 20 0 (a) Give the electronic configurations of the elements. (a) Choose the letters that represent 30 31(a neutral atom of a metal Gi) a neutral atom of a non-metal (i) a pair of isotopes (iv) a cation () an anion () Which particles have noble gas electronic configurations? Specify the electronic configuration in each case. (©) Give a formula to the compound formed between () Canad (i) E and hydrogen (ii) Cand oxygen (iv) A and B In each case, say whether the compound will be an acid, a base. orasalt 6) The symbols of the elements of atomic number 11-18 inclusive are: Na, Mg, Al, Si, P, S, Cl, Ar (a) Classify the above elements into metal, semi-metal or non-metal, (b) Give the name and structural formula of a covalent hydride of ‘two of the elements (©) Give the name and structural formula of an ionic chloride of ‘h9o of the elements. (@) From the list above, name an element which does not readily form compounds. 7) Give electronic diagrams to distinguish between the atom, molecule and ion of (a) oxygen (6) Muorine 8) Draw electronic zrams for the following compounds: (@) sodium hydride NaH (0) methane CHa (©) ammonia NH (8) water HO (@) hydrogen chloride HCL (O) hydrogen sulphide HS (@) tetrachloromethane CCl, (h) carbon dioxide CO; (i) potassium fuoride KF (@. sodium oxide NaxO (k) calcium oxide C20 @) sodium hydroxide NaOH (mm) phosphorus(IIl) chloride PCl, (a) silane Sill, (0) phosphine PH, (P) dichloromethane CH,Cls 32 9) Draw electronic formulae (showing the outer shell electrons only) of the following compounds: G@) silane Sift, () calcium chloride CeCl, (c) phosphorus(III) chloride PCI, (4) carbon dioxide CO, (@) carbon disulphide CS, (0 lithium oxide Liz 10) A metal A (atomic number: 11) burns in chlorine to produce a white, solid chloride B By means of electronic diagrams, illustrate the arrangement of electrons in A both before and after the reaction. Discuss the following properties of B and account for them as far as possible: (@) Melting point (b) Solubility _(¢)_ Electrical conductivity 11) When potassium chlorate decomposes to form potassium chloride and oxygen, (a) show by diagrams the electronic structure of the products, (b) state the properties you would expect the products to have because of their particular type of bonding. (HKCEE) 12) When sodium sulphite is warmed with an excess of dilute hydrochloric acid, a choking gas X is evolved. The resulting solution on evaporation ives a white crystalline solid Y. (@ Name X and ¥. (b) Write an equation for the reaction involved. (©) Draw a diagram to show the electronic structure of Y. _ (HKCEE) 13) Four elements A, B, C and D of atomic numbers less than 20 have respectively electronic configurations (X].1, [X] 4, [X].6 and (X].7, where [X'] is a noble gas configuration and 1, 4, 6 and 7 are the number of electrons in the outermost shells of their respective atoms. (a) Of the 4 elements, predict which will be volatile and which will conduct electricity. (b) Predict which of B, Cand D will react with A readily. (©) A reacts with C and D to form F and F respectively, while B reacts ‘with C to give G. Draw diagrams to show the electronic structures you would expect of compounds £, F and G. (The noble gas configuration [X] can be represented by a circle in diagrams) (HKCEE) 3314) (a) Am element X forms, with an element ¥ whose atoms have four electrons in their outermost shells, a compound of the structure efofo where © represents a noble gas structure. (i) How many electrons are there in the outermost shell of X? Gi) Suggest two elements which X can represent. (b) If chlorine reacts with magnesium and hydrogen to form P and Q respectively, state the nature of the bonds formed and draw 2 diagram showing the electronic structure you would expect for each of the products. (HKCEE) 15) If Z is the atomic number of argon, the atomic number of element X is (Z = 1),and that of element Vis (Z.+ 1) (a) Name X and ¥. (b) Using electronic diagrams only, show how the electronic structure of argon is attained, (i) when X and ¥ combine with each other, Gi) when X exists in the form of a molecule. (HKCEE) 16) Elements X, ¥ and Z occur in the same period of the Periodic Table. ‘They have respectively 1, 6 and 7 electrons in the outermost shells of their atoms. (@) Of the three elements which one would you suspect to have the tendency to exist as diatomic molecules at room temperature and pressure? Why? (b) Which of the elements possesses the least ability to form anions? (©) Draw a diagram to show the electronic structure of the compound which is formed when (@ X combines with Z Gi) ¥ combines with Z Gi) X combines with ¥. (@) Which of the compounds formed in (c) will have the lowest ‘melting point? Why? (CDC. Sample Question) 34 17) (a) Name two compounds, one containing hydrogen, oxygen and sodium, and the other containing hydrogen, oxygen and sulphur. (b) Draw an electronic diagram of the sodium compound mentioned in. (©) What are the changes in bonding, if any, when the two compounds ‘mentioned in (a) are separately dissolved in water? (@) Which of the two compounds mentioned in (a) has the higher smelting point? Explain briefly the difference between the melting points of the {wo compounds. (HKCEE) 18) A compound X2¥ is formed between a metal X and a non-metal Y, All ions in the compound have the argon electronic configuration. (a) Give the (i) structural formula (ii) electronic formula of the compound, (b) Give the electronic configurations of the atoms of (j) X and wy. (c) Name elements X and Y. (@ Would you expect the compound to conduct electricity in () solid state i) liquid state (ii) aqueous solution? 19) The diagram below shows part of the ionic lattice for a compound with the formula XY. The anion in this structure is ¥"". © cation Q anion ¥,7 (@) How many atoms of ¥ are there in one Ya?" ion? (©) What is the charge on the cation inthis compound? (©) Which of the following statements about the ionic lattice is true? (i) There are twice as many cations as anions in the lattice ) There are twice as many anions as cations in the lattice i) There are equal numbers of cations and anions inthe lattice (@ State whether or not the fonic compound magnesium chloride (MgCI,) could exist in the structure shown above. Give a reason for your answer. 38SHAPES OF SIMPLE MOLECULES & IONS SHAPES OF SIMPLE MOLECULES A molecule always consists of 2 or more atoms joined by covalent bonds (except molecules of noble gases). The shape of a molecule is a description of the way the atoms occupy space. A diatomic molecule (eg. Cl-Cl, HCl, O=0, N=N) must be linear in shape, since the centres of the two atoms are in a straight line. Thus in the following discussion, ‘we shall only consider shapes of molecules with three or more atoms ‘Electron cloud’ repulsion theory The ‘electron cloud’ repulsion theory can enable us to explain and predict shapes and approximate bond angles of many simple molecules ‘The main points are: (1) An ‘electron cloud’ may be a single bond, double bond, triple bond or lone pair. (2) ‘Electron clouds’ (all negatively charged) try to get as far apart from fone another as possible because of mutual electrostatic repulsion, (3) Lone pairs of electrons exert a greater repelling effect than bond pairs do. It follows that: lone pairone pair ., lone pair-bond pair, bond pair-bond pair repulsion repulsion repulsion 36 Prediction of molecular shapes and bond angles Different number of ‘electron clouds’ in a molecule will give rise to different arrangements in space. A brief summary is given below: ‘Number of ‘electron clouds" in outermost ‘Shape Sketch shell of ‘central atom’ 2 linear 3 trigonal planar 4 tetrahedral 109.53 square planar (uncommon) —-R ‘The aforesaid can be illustrated by the following example. Example 3.1 Deduce the shapes and approximate bond angles of the following ‘molecules: (a) CH, — (b) NHs —(c) HO (d). CS 37The steps are outlined below: Seps cH WH 4,0 os 1) Select the ‘central atom’ of the c N ° c ‘molecule 2 From the suctunl] Ht formula, find out | the numberof [AFH ‘electron cloud | H inthe outermost | 4 single bonds] _ 3 single bonds stetlof thee) Olone pair |#) Tone pair ented atom PE | ‘eclouds) | 4 ecloude 2 single bonds +) 2lone pairs 4 e clouds 2 double bonds +) Otone pair Pe clouds 3 Find out the furthest arange- ment of ‘electron clouds" tetrahedral | tetrahedral tetrahedral 4 Deduce the ‘theoreteal bond angle from the 109.5° 109.5° seometry of this basic arrangement 109.5° 10" 5 Find the shape of molecule with respect to atoms (in doing s0, any Tone pais present ‘smor taken into account) V-shaped (angulr, bent) S=c#s 6) Estimate the ‘approximate bond | H—C-H H-N-H angles allowing angle angle for greater = 109.8° = lor repelling effect 4-0-8 angle = 10s" cof lone pairs Note: C> stands for a lone pair of electrons. 38 REPRESENTATION OF 3-DIMENSIONAL STRUCTURES ON PAPER To draw 3-dimensional molecules on paper, the following symbols for electron pairs are often used: bond in plane of paper bond going behind paper ‘bond coming out of paper 20) The dissociation of an fonic compound Xm Yq (formula mass = 400) in water may be represented by the following equation: XmYa——> mx™ + n¥™ * Optional question 63If 50 g of XqYq are dissolved in water and the solution is made up to 500 cm?, calculate (@) the number of moles of X®* ions in 1 cm? of the solution (©) the total number of moles of X* ions and ¥™" ions in 100 cm® of the solution MASS ANALYSIS OF (©) the volume of solution that contains 0.1 mole of ¥™~ fons. 21) (@) Calculate the number of atoms in 1g of 1*C isotope. (Mass of COMPOUNDS cone atom of '7C = 2 X 10? g) Hence calculate a value for Avogadro's Number. (b) A 150 cm? flask is filled with pure oxygen at room temperature and pressure. How many oxygen molecules are there in the flask? (Assume the molar volume of a gas at this temperature FORMULAE OF COMPOUNDS and pressure = 24 dm*) : The empirical formula of @ compound is the formula which shows (©) The same flask is then completely filed with water at room the simplest integral (whole number) ratio of the number of atoms or temperature, Calculate the number of water molecules present. ee ed el een eee oe The molecular formula of a compound is the formula which shows the actual number of each kind of atom in one molecule ofthe compound. Note: This kind of formula is applicable only to molecular compounds.) ‘The structural formula of a compound is the formula which shows how the constituent particles are joined up in the simplest unit of the compound. Fer a molecular compound, the structural formula shows the arrangement of ators in a molecu. For an ionic compound, the structural formula shows the ratio of the number of fons present and aso the charges carried by them Examples ne Emre eae ‘Structural Carbon dioxide co, co; Ethene CH; CHa Bthyne cH CoH “a 65Empirical Molecular ‘Structural eee formula. formula formula Ho stihaneacid OHO, HCC 4 o 4H ‘Methyl methanoste CHO C440, HOCH 4 ‘pou Ammonium chloride NHAC —inapleble | H-N-H | oF 4 Iron(ll) sulphate FeSO,, 4 inapplicable Fe2"S0,2" 7,0 T-water Sulphuric acid H, SO, H,SO, % COMPOSITION FROM FORMULAE From the formula of a compound, we can easily work out the percentage by mass of each element in the compound. In general Fraction by mass of clement A in compound = Homic mass of A X no. of atoms of A in formula formula mass of compound Percentage by mass of element A in compound atomic mass of A X no. of atoms of A in formula Tormula mass of compound ae * Different compounds may have the same empirical formula and molecular formula (ee p.283 for details) Example 6.1 Guleulate the percentage by mass of sodium, carbon, oxygen and hydrogen in sodium carbonate-10-water, NazCOs.10H30. Formula mass of NazCOs.10H;0 nu CO 10140 = 2324124 16X 3+ 1001 X 2+ 16) = 286 by massof No = 23%2 x 100% = 16.1% soymacte = 22x 10m = 428 sry massoto = XE*1) x 109% = 12.7% toby massof H = 1X2 x 100% = 70% 286 Example 6.2 Find the mass of water of crystallization in 7.5 g of hydrated copper(I) sulphate, CuSOs.5H20. Mass of water of crystallization mass of ti hydrated fraction by mass of H, 0 in the hydrated salt a a Find the mass of magnesium needed to prepare 40.6 g of magnesium chloride-6-water, MgCl. 6H, 0. Fraction by mass of magnesium in MgCl, .6H; 0 7 zt -# * FHS K2+O0X2+16) 203 ‘Mass of magnesium needed to prepare 40.6 g of MgCl; .6H,0 = mass of magnesium present in 40.6 g of MgClz.6H; 0. 24 = 406X355 = 488 67Example 6.4 Find the mass of chlorine in (a) 2 moles of phosphorus(It1) chloride PCts [b) 4.8 dm? of hydrogen chloride HC! (measured at room conditions) (c) 200 em? of 1.50 M BaCt; solution. (@) Since 1 mole of PCL; contains 3 moles of CI atoms, no, of moles of C1 atoms in 2 moles of PCI = 3X 2 Mass of chlorine = no, of moles X molar mass 6X 355 = 213g given volume ‘molar volume - 48 ore Since 1 mole of HCI contains 1 mole of C1 atoms, ‘no. of moles of Cl atoms = 0.20 Mass of chlorine = 0.20 X 35.5 = 7.1 g (b) No. of moles of HCl gas = 0.20 (© No. of moles of BaCly in the solution = molarity X volume of solution (in dm*) 200 1.50 x 20 = 0300 Since 1 mole of BaCls contains 2 moles of CI ions no. of moles of CT ions in the solution = 0.300 X 2 = 0.600 Hence mass of chlorine(CI" ions) = 0.600 X 35.5 = 21.3 g ATOMIC MASS FROM FORMULA Atomic mass of an element may be calculated from formula of its compound. Study the following example. Example 6.5 The chloride of a metal M has the formula MCI, and contains 34.5% by mass of M. Find the atomic mass of M. | Let the atomic mass of M_ be Ar. Atomic mass of metal At 34s Formula mass of MCI, ~ A, +3553 ~ 100 = Ay = 561 Hence atomic mass of the metal M is 56.1 Example 6.6 5.6 g of a metal M combine with 2.4 g of oxygen to form an ‘oxide with the formula M03. What is the atomic mass of M? Let the atomic mass of M be Ar. Mass of M_in compound | 2A; _ $6 Mass of oxygen in compound ~ 16X3 ~ 24 =A = 56 Hence atomic mass of the metal M is 56. Example 6.7 A crystalline sale of formula M,S,0,.5H20 is found 10 contain 36.3% by mass of water of crystallization, Calculate (a) the formula mass of the hydrated salt (b) the atomic mass of the metal M. Go Masol mater of cxytalization |__S(1 X 2+ 16) ‘Mass of hydrated salt’ Tormula mass of hydrated salt = 363. 100 = Formula mass of hydrated salt = 248, (©) Let the atomic mass of M be Ar. Formula mass of hydrated salt = 2A, +32X 2416 X 345(1X 2416) = 248 2A = B Therefore the atomic mass of M is 23.FORMULAE FROM COMPOSITION ‘The empirical formula of a compound can be determined experi: ‘mentally by finding its composition by mass. To determine the molecular formula, we need to know both the empirical formula and molecular ‘mass of the compound. Molecular masses of gases and volatile substances can be found froin vapour density: Molecular mass = 2 X vapour density (ote: For definition of vapour density, see p. 113.) Steps to find empirical formulae from composition by mass 1) Find mass of each element in a certain mass of the compound. tn case percentages or fractions by mass of elements are given, asume these values to be masses in gram, (These are relative masses of clements.) 2) Divide each mass by molar mass of the element to give number of moles of atoms 3) Divide all values obtained in (2) by the smallest of them, This ives relative numbers of moles of atoms. 4) If the numbers obtained in (3) are still not all whole numbers, then ‘multiply all of them by the smallest suitable integer so as to make them all whole numbers 5) Insert these numbers after the symbols of the respective elements to sve the empirical formula, Example 6.8 A hydrocarbon M contains 85.7% carbon. Its vapour density is 28. Calculate the empirical formula and molecular formula of M. (HKCEE) Since M is a hydrocarbon, it contains carbon and hydrogen only. It contains 85.7% carbon and (100 ~ 85.7) = 14.3% hydrogen by mass, Carbon Hydrogen Relative masses (in g) 85.7 143 Relative no. of moles of atoms a 143 ‘molar mass) ae 43 13,5 Cave by he sates umber) 14 70 ‘The empirical formula of M is thus CH Let its molecular formula be (CH,)q, where a isan integer. Then n(12 +1 X 2) = M, of M vapour density of MX 2= 28 X 2 = 56 56 4 ‘The molecular formula of M is (CH,)s ie. CsHs. Note: Experimental errors would probably result in a small deviation from whole numbers when calculations such as those outlined above are carried out. It is an accepted practice to ‘round off” these values to the nearest whole numbers. However, care must be taken in doing this, eg. 3.03 can be taken to be 3 but 3.3 cannot be taken as 3, Example 6.9 A compound containing only carbon, hydrogen and oxygen gave the following results on analysis: 0.81 g of substance gave 1.32 g of carbon dioxide and 0.45 g of water, Find the empirical formula of the compound. If its vapour density was 80, find also its molecular formula, In this question, we are not given the relative masses of the constituent elements directly, so we have to find them out first. 2 Fraction by mass of C in CO 1x2 18 Fraction by mass of H in H,0 = Since the C in CO and H in HO all came from the compound, eee take mass of C in compound = 1.32 X a” 0.36 g; poe 18 the rest of the compound must be oxygen, mass of H in compound = 0.45 X 4 = 0.05 g; mass of O in compound = 081 ~ 0,36 ~ 0.05 = 0.40 g 1Now proceed to find the formulae as follows Carbon Hydrogen Oxygen Relative masses (in g) | 0.36 (0.05 0.40 Relative no. of moles of atoms 0.36 mit | 9386 = og 025 molar mas) [72 ~ 0080 Caivide by the [0.080 005, [005 | mallet no.) | 0.025, 0.025 0.025 (outily bythe smallest possible e . . Beigua [12XS=6 [2xS=10 1XxXs=s to turn al values to whole numbers) (ote: As explained before, we cannot take 1.2 to be equal to 1, otherwise the empirical formula would be CH,0.) Empirical formula of compound is Cs HyoOs Lot its molecular formula be (CeH1oOs Jn, where n is an integer. M, of (CoHioOs)n = 2X 80 n(12 X 6+ 1X 10+ 16 X 5)=2 x 80 162n = 160 nél Molecular formula of compound is Cs HyoOs Example 6.10 10.0 g of hydrated iron) sulphate, FeSOs.nt1;0, on strong heating, ge 4.53 g of water. Find the value of n. FeSO. 0 Relative masses (in g) 547 453 Relative no, of moles mas. 453 ‘molar mass) 18 (Givide by the smallest no.) 0036, | 0252.5 0.036 0.036 Note: In this case, relative numbers of moles of compounds (not elements, as in previous examples) are to be found. Example 6.11 A hydrated salt of magnesium contains 48.78% by mast of the anhydrous salt. The anhydrous salt has the following percentage composition by mass: magnesium: 20.00%; sulphur 26.67%; oxygen: 53.33%. Find empirical formula of the hydrated salt, Firstly, we have to find empirical formula of the anhydrous salt ‘Magnesium — | Sulphur ‘Oxygen Relative masses (in g) | 20.00 2667 53.33 Relative no. of moles of atoms mass 26.67 _ 5333 ) 833 | 257 = 0.833 | I = 3.33 (aivide ty the 9.833 smallest no.) 0833 Empirical formula of the anhydrous salt is MgSOs. Let empirical formula of the hydrated salt be MgSO. .nH, 0. Formula mass of MgSO,.nH,0 = 24+32+16X 4+n(1 X 2+16) 120 + 18n Fraction by mass of anhydrous _ 120 _ 48.78 salt in MgSO,.nH1;0 120+ 18a ~ 100 = ne7 Hence empirical formula of the hydrated salt is MgSO..7H,0. Example 6.12 A colourless organic liquid, L, contains 40.00% of carbon, 6.67% Of hydrogen and 53.33% of oxygen. 1.50 g of L, when vaporized, is found 10 cecupy 560 cm? at s.tp. Calculate the empirical and molecular formula of L. (HKCEE) BCarbon Hydrogen Oxygen Relative masses (in g) | 40.00 6.67 53.33 alae no. of moles ofatoms 40. 3333 ( olar mass? oad 16 aes 5 733 dite ne [ESS 333 tmae'no) | 333"! 333 The empirical formula of L is CH,O. 1.50 g of L occupied 560 cm? at stp. while 1 mole of L occupied 22 400 em? at s.tp. 22.400 560 ~ Let the molecular formula of L be (CH; 0)n. a(l2+#1X2+16) = 60 n=2 Molar mass of = 1.50 X ‘The molecular formula of L is C;H Ox Example 6.13 A metal M forms two chlorides A and B which contain 55.9% and 65.5% by mass of chlorine respectively. The empirical formula of A is found to be MCI. Determine the empirical formula of Biwithout having to find the atomic mass of M). ‘The % composition by mass of the chlorides are calculated. The values are expressed in g unit and tabulated below: ‘Metal M Chlorine Chloride A 44.18 3598 Chloride B 3459 6558 If mass of M in chloride B is the same as that in chloride A (Le. 44.1 g) mass of chlorine in chloride B will be (by proportion) equal to 44.1 655 x44 = 93.7 ¢ 4 ‘Therefore for the same mass (hence same no. of moles) of M, mass of chlorine in chloride B__ no. of moles of chlorine in chloride B ‘mass of chlorine in chloride A~ no. of moles of chlorine in chloride A 83.7 3 Bae 1S of > Since formula of chloride 4 is given to be MCIz, formula of chloride B should be MCly, EXERCISE 6 COMPOSITION FROM FORMULAE 1) Calculate the percentage composition by mass of the following: (a) Carbon in methane, CHy (b) Sulphur in anhydrous sodium sulphate, NazSOx (©) Water in sodium carbonate-10.water, NazCO3 10H; 0 (@) Oxygen in iron(I!) sulphate-7-water, FeSO,..7H; 0 2) Find the masses of (a) carbon in 10 g of methane, CH, (b) sulphur in 0 g of anhydrous sodium sulphate, Na;SO, (©) water in 100 g of sodium carbonate-10-water, Naz CO.10H; 0 (@) oxygen in 18.8 g of iron( il) sulphate-7-water, FeSOy.7H;0 (€) chlorine in 2 moles of iron(II) chloride-6.water, FeCls 6H; 0 (©) water in 1.25 moles of calcium chloride-6-water, CaCl; .6H;0 3) What mass of metal is present in 10 moles of (@) CaCO, (b) FeCl, (©) Kx Cr20,? 4) How many moles of each constituent ion are present in 9.5 g of MgCl, ? 5) What mass of oxygen would be needed to form (a) 2 moles of CO; (©) 46 g of NO, (©) 2.24 dm? of SO, (measured at stp.) (@) 602 X 10? formula units of MgO? 6) Calculate the mass of sodium ions in 250 cm? of 0.100 M NaCOs solution, 57) Which is the cheaper source of sodium carbonate? ‘A. Anhydrous sodium carbonate NazCO3 at $2 per kg. B. Washing soda crystals Na,CO3.10H,0 at $1 per kg. 8) What mass of nitrogen is present in that mass of sodium nitrate (NaNO) which contains 100 g of sodium? 9) What mass of water of crystallization is present in that mass of sodium carbonate-lO-water (NazCO3.10H,0) which contains 4.6 g of sodium? ATOMIC MASSES FROM FORMULAE 10) A metal oxide MO contains 79.87% by mass of the metal M. Find the atomic mass of M. 11) 26.88 g of a metal chloride MCI contain 5.68 g of chlorine. Find the atomic mass of the metal M, 12) 290 g of a metal oxide (§Mz0) decompose completely into its elements on heating to give 150 cm? of oxygen measured at room conditions. Calculate (a) formula mass of M0 (b) atomic mass of M. 13) MCI, contains 44.1% by mass of M. Find the atomic mass of M. M also forms another chloride MCly. Find the percentage by mass of chlorine in the higher chloride. 14) 2.86 g of a hydrated salt of formula M;COs.nH,0 were heated to constant mass, It was found that 1.06 g of solid remained. Calculate the percentage by mass of water of crystallization in the salt. If the formula mass of the hydrated salt is 286, find n and the atomic mass of M. FORMULAE FROM COMPOSITION 15) Find the empirical formulae for compounds having the following composition by mass: (@) 923% carbon, 7.7% hydrogen (©) 86.6% lead, 13.4% oxygen (©) 15.79% aluminium, 28.07% sulphur, 56.14% oxygen (@) 40.67% carbon, 23.73% nitrogen, 27.13% oxygen, 8.47% hydrogen. 16) 5 g of sulphur, after combustion, give 10 g of one of its oxides. Find the empirical formula of this oxide. 16 17) 19.85 g of an element M combine with 25.61 g of oxygen to form an oxide. Given only that the relative atomic masses of M and oxygen are 31 and 16 respectively, deduce the simplest formula for this oxide. (KcEE) 18) Yellow ammonium sulphide (NH,)zSx contains 72.72% by mass of sulphur. Find x. 19) Find the empirical formula of a hydrated salt containing 37.11% of copper and 41.68% of chlorine by mass (the rest being water of crystallization). 20) If the formula of @ hydrate is MgSO,.xH,0 and the percentage by mass of water of crystallization is $1.22, what is the value of x? 21) 2.48 g of NazCOs.nH0, on strong ‘heating, left 2.12 g of the anhydrous salt. Find the value of n. 22) A hydrate contains 16.08% sodium, 4.20% carbon, 6.99% hydrogen and 72.73% oxygen by mass. If all the hydrogen atoms of the hydrate are in the form of water of crystallization, determine its empirical formula, 23) 0.166 mole of a hydrated salt, on strong heating, gave 17.94 g of water. Find the number of moles of water of crystallization in one mmole of the hydrated salt, 24) 20 g of a crystalline salt contain 9.73 g of water of crystallization If the percentage composition by mass of the salt is 8.11% aluminium, 14.41% sulphur, 72.07% oxygen and 5.41% hydrogen, derive the formula of the salt 25) 4.8 g of a metal M of atomic mass 24 form 19 g of chloride with excess of hydrogen chloride on heating. (@) What mass of the chloride contains 1 mole of M? (b) What_mass of chlorine is present in that mass of the chloride in)? (©) How many moles of chlorine atoms combine with 1 mole of ‘Min this chloride? (@) Deduce the empirical formula ofthe chloride. 126) 1.2 g of a gaseous hydrocarbon Z are burnt completely in excess of dry oxygen in a suitable apparatus, and the resulting gas is led through concentrated sulphuric acid, The acid increases in mass by 186 g. Calculate the empirical formula of Z. 2.0 dm? of Z when measured at s.t.p., weigh 5.178 g, Deduce the ‘molecular formula of Z, (HKCEE) 27) 1.200 g of a compound containing only carbon, hydrogen and oxygen gave on complete combustion 1.173 g carbon dioxide and 0.240 g water. Vapour density of the compound was determined to be 45. Find the empirical and molecular formula of the compound 28) Complete combustion of 1.86 g of an organic compound gave 2.64 g of carbon dioxide and 1.62 g of water as the only products, If the density of the compound at s.t.p. was found to be 2.77 gdm", find its molecular formula. 29) A compound Z contained only nitrogen, hydrogen and chlorine, On quantitative decomposition in aqueous solution, 3.170 g of Z Jiderated 1109 cm? of nitrogen at room conditions. Addition of aqueous silver nitrate to solution containing 1.585 g of Z caused the formation of 3.315 g of silver chloride (AgCI). Deduce the simplest formula of Z, 30) The diagram shows the apparatus to be used in an experiment to determine the formula of a gas X which contains two elements. was asbestos wool copper syringe A oxide Il i= heat 8B 100 om? of gas X were passed slowly over red hot copper(I) oxide in tube B. The following results were obtained. (All gas volumes ‘were measured at room temperature and pressure) Weight of tube B before the experiment = 20.10 g Weight of tube Bafter the experiment = 20.00 g A colourless liquid was collected in tube C 50 cm? of nitrogen were collected in syringe D. (@ Describe simple chemical test which would show that the colourless liquid collected in tube C contained water. (b) What are the two elements in gas X? (©) Why did tube B lose weight? (@ Calculate the gain in weight of tube C. (©). What is the mass of nitrogen collected in syringe D? (Molar volume at room temperature and pressure can be taken as 24dm*) (0) Whats the mass ofthe 100 cm? of gas Xin syringe A? (@) What is the mass of one mole of gas X? (@) Find the empirical formula of gs X (© Deduce the molecular formula of gas X. cuKcee) MISCELLANEOUS PROBLEMS 31) The following diagram shows the apparatus used in an experiment to determine the formula of black copper oxide, excess town pas burning in small flame ae ee FS cick copper oxide heat Town gas was passed over the oxide before heating began. During heating, the copper oxide changed colour from black to light brown, After some time, heating was stopped, but town gas was allowed to pass over the copper until it was cold, The results were as follo. 9Mass of tube = 20108 Mass of tube and copper oxide = 22.68 g Mass of tube and copper 2.168 (@) Why is town gas bumt at the jet after it has passed over the copper oxide? (b) If the flow of town gas had stopped at the same time that the heating was stopped, would the final mass be (A) larger than 22.16 g (B) 22.16 g (C) smaller than 22.16 g? (©) What mass of copper oxide was used? (@)_ What mass of copper was formed? (@) What mass of oxygen had therefore combined with the copper in the original mass of copper oxide? (©) What happens to this oxygen during the experiment? (@) How many moles of copper were formed? (h) How many moles of oxygen atoms were combined with the copper? (@)_ What is the empirical formula of the black copper oxide? 32) In an experiment, two heated oxides X and ¥ of the same metal M were completely reduced by hydrogen. The results were recorded as follows: (1) Mass of oxide X = 42.9 g, mass of metal M left = 38.1 g (2) Mass of oxide ¥ = 15.9 g, mass of metal M left = 12.7 5 If the formula of oxide X is M;O, what is the formula of oxide ¥? 33) A hydrated salt contains 10 moles of water of crystallization per mole of crystals and the percentage by mass of anhydrous salt is 37.06. Find the molar mass of the hydrated salt. 34) By analysis, 23 g of a compound of formula Xz¥Ox were found to contain 13 g of X, 2g of ¥ and 8 g of oxygen. Calculate (@) the mass of X that combines with 16 g of oxygen in the ‘compound (©) the relative atomic mass of X (©) the mass of ¥ that combines with 1 mole of oxygen atoms in the compound (@) the relative atomic mass of ¥ (©) the molar mass of the compound. 35) A pupil was given 2 bottle containing a carbonate which was known to have the formula MCOs. He weighed out several samples of the carbonate and added $0 em* of 0.1 M hydrochloric acid solution to each. The reaction is represented by the following equation: MCO4(s) + 2HC(aq) —> MCI,(aq) + COs(@) + H20(2) The volumes of CO, collected were corrected to stp. Mass of MCO, (ing) Volume of C03 | >2.5 | 335 | 445 | $60 | $60 | 60 | $60 | 56.0 at stp. (inem?)| 225 | (0.10 | 0.15 | 0.20 | 0.25 | 0.30 | 0.35 | 0.40 | 0.45 @) Plot these points on a graph of volume of carbon dioxide (on vertical axis) against mass of MCOs.. (b) Determine the formula mass of MCOs (©) What isthe atomic mass of M7? (@) Whatis the identity of MCO,? 817 EQUATIONS WHAT AN EQUATION IS ‘An EQUATION is a statement, in symbols, which shows the relative numbers of particles involved in a chemical reaction. The symbols used are formulae of reactants (reacting substances) and products (substances produced). ‘An equation is in fact a precise quantitative statement representing a reaction, It tels us not only the identity of reactants used and products formed, but also the stoichiometry of the reaction, i.e, the relative number of moles of substances involved. For example, the reaction between magnesium and oxygen to produce magnesium oxide can be represented by the following equation: 2Mg + 0; ——> 2MgO reactants product relative no, of moles 2 1 2 Physical state symbols can be included in equations to indicate whether substances involved are in solid(s), liquid(®), guseous(g) or aqueous(aq) phase. Thus the above equation can be rewritten as: 2Mg(s) + 03(@) —+ 2Mg0(6) physical state symbols Generally, equations must be balanced. In a balanced equation, the number of atoms of a certain kind on the reactant side must be equal to the number of atoms of that kind on the product side. (The atoms may be free, charged or in molecules.) Equations are balanced by putting appropriate numbers (stoichiometric coefficients) before formulae of 82 reactants and products. In the above equation, the numbers in front of Mg, O2 and MgO are 2, 1 and 2 respectively. Note that ‘I" is usually understood and can be left out ~ Oy is writen instead of 10 INFORMATION FROM AN EQUATION Information which can be obtained from an equation may be illustrated by an example: When a gas jar of hydrogen sulphide is inverted over a gas jar of chlorine ard the gases are allowed to mix, steamy fumes of hydrogen chloride and a yellow precipitate of sulphur will be formed. The reaction is represented by the following equation: H,S(g) + Cl:(g) —> 2HCI(g) + S(s) The following information can be obtained from the given equation (1) HyS,Cl; and HCI ate in gaseous state, S is in solid state. @) 1 mole of HyS reacts with 1 mole of Cl; to produce 2 moles of HCl and I mole of 8. @) Since | mole of any substance contains the Avogadro Number of particles of that substance, it follows from (2) that 1 molecule of H,S reacts with 1 molecule of Cl; to produce 2 molecules of HCI and 1 molecule of . (4) In terms of mass, 34 g of HyS react with 71 g of Cly to produce 73 gofHICl and 32 g of S (or other values in this ratio). (©) By Avogadro's Law, mole ratio of gases can be converted to volume ratio. So under the same conditions of temperature and pressure, 1 volume of H§ reacts with 1 volume of Cl, to produce 2 volumes of HG. (Volume of solid or liquid is usually negligible when compared with volume of gas. Thus the volume of solid sulphur is neglected when compared with volumes of hydrogen sulphide, chlorine and hydrogen chloride.) IMPORTANT POINTS TO BE NOTED CONCERNING AN EQUATION (1) Total number of moles of reactants is not necessarily equal to total number of moles of products Note: In the example mentioned, 1 mole of H,S reacts with 1 mole of Cl; to give 2 moles of HCl and 1 mole of S, thus there are 2 moles of reactants and 3 moles of products in this case, 832) Total number of atoms of a certain kind on the reactant side must be equal to total number of atoms of the same kind on the product, side. (3) Total mass of reactants must be equal to total mass of products. ‘This is, in fact, what the Law of Conservation of Mass states. (4) Total volume of reactants is not necessarily equal to total volume of products. For example, 2NO(G) + On(g) —* 2NOs(@) 3 volumes 2 volumes IONIC EQUATIONS Equations which include ionic formulae are called ionic equations. ‘An ionic equation specifies only the particles which take part in the chemical reaction and omits anything which remains unchanged. ‘An ionic equation must be balanced with regard to charges as well ‘as number of particles, that is, the net charge on the reactant side must be equal to that on the product side. In order to write an ionic equation comectly, a good understanding of the bonding and solubility behaviour of reactants and products, and the type of reaction involved would be required. (lonic equations of the redox type will be discussed in detail in Chapters 10 and 11.) Example 7.1 Write an ionic equation to represent the reaction which takes place between (a) aqueous solutions of barium chloride and sodium sulphate {6} magnesium metal and dilute hydrochloric acid. (a) BaCl, and Na,SO, are ionic compounds, both soluble in water. In aqueous solution, BaCl; exists as Bu?“(aq) and C1(aq) ions, while Naz$Os as Na°(aq) and $04? (aq) ions, all of which are mobile. Upon mixing, Ba?“(aq) and $0," (aq) ions would come together to form 1 precipitate (Since BaSO, is insoluble in water). But CI(aq) and Na‘(aq) ions are as freely mobile at the end as they were at the beginning of the reaction — they are spectator ions, having not participated in the reaction. Thus the ionic equation is: Ba*“(aq) + $O,7(aq) —> BaS0, (6) Note net charge on the reactant side = (+2) + (-2) = 0; net charge on the product side = 0 (b) Dilute HCI contains H'(aq) and CI'(aq) ions. The H'(eq) ions can react with an electropositive metal to give Hz gas. Hence the following ionic equation can be worked out: Mg(s) + 2H"(aq) —> Me*(aq) + Ha(@) (Note that C1(aq) ions are spectator ions in this case.) FINDING EQUATION FROM EXPERIMENT Equations can be determined experimentally by finding the relative number of moles of reactants and products. The fact that total number of atoms of any kind written in an equation must balance makes the experimental determination of equations much easier, as ilustrated by the following example. Example 7.2 Write an equation for the following reaction: 10.6 g of sold sodium carbonate (NazCOs) required 100 om? of 2.00 M hydrochloric acid (HQ) for complete reaction, 2400 em? of carbon dioxide (measured at room conditions) being produced. Upon evaporation of the resulting solution, 11.7 g of sodium chloride (NaCl) were obtained, Reactants: NazCO3, HCL Products: NaCl, CO; ete. mass ‘molar mass No. of moles of NazCOs 0.100 No. of moles of HCl = molarity X volume (in dm?) 100 = 2.00 x = 0.200 No. of volume Yo. of moles of COs = “rofar volume under the same conditions 2400 ~ 24000 ~ 0100 x uz io. of moles of NaCl = = 0.200‘Thus ratio by moles of NazCO3 : HCI : NaCl: CO; = 0.100 : 0.200 : 0.200: 0.100 = 1:2:2:1 We now have NazCO; + 2HC|—+ 2NaCl + CO, +... ‘IH;0° is added to the right hand side of the above ‘equation’ in order to balance the number of hydrogen and oxygen atoms. Na,CO3 + 2HClL—+ 2NaCl + CO, + H20 Putting in physical state symbols, we have the required equation: 1NaCO4(6) + 2HCI(aq) —> 2NaCI(aq) + CO2(g) + H,0(®) Example 73 50 em? of 0.10 M HCI reacted exactly with 12.5 cm? of 0.20 M PO(NOs), solution 10 give a white precipitate of PbCly. Deduce the ionic equation for the reaction. Reactants : HCI, Pb(NO3)2 5 products : PbCl, ete. soba No. of moles of HCI = 0.10 X 7555 = 0.0050 No. of moles of CI’ ions = 0.0050 = 125 No. of moles of PO(NO3), = 0.20 X Tp5 = 0.0025 No. of moles of Pb** ions = 0.0025 Only Pb*{aq) ions and C(aq) ions take part in the reaction; NOs (aq) fons and H'(aq) ions are spectator ions Ratio by moles of Pb™(aq) ions : CY(aq) ions = 0.0025 : 0.0050 1:2 ‘The ionic equation is: Pb*(aq) + 2CI(aq) > PbCI2(s) Example 7.4 X and Y are metals. X displaces Y from a solution of the nitrate of ¥. When several samples of powdered X of known masses were added 10 excess aqueous solutions of the nitrate of Y in separate tests, the ‘masses of Y precipitated were weighed out. The results are shown in the following graph. 86 0020 040 060 080 10 12 Masof Xing (a) The experiment was repeated using another mass of X and 3.0 g of Y were obtained. How many grams of X were used? (6) What mass of ¥ would be produced by the reaction of one mole of X? (Atomic mass of X= 65) (c) How many moles of Y would be produced in (b)? If the charge of an ion of ¥ is 1+, what is the charge of an ion of X? (Atomic mass of Y = 108) (d) Write an ionic equation 10 represent the reaction that occurred. (@) Mass of X = 0.90 g (read from graph). (©) Using data from (a) and by proportion, 65 mass of ¥ = 3.0 X a5 = 217g : 217 © No. of moles of ¥ = Tog = 2.009 #2 Since 1 mole of X can displace 2 moles of Y from the salt solution, ‘charge on an ion of X should be double that on an ion of Y. Charge on an ion of X = 2+ (@) The onic equation is: X() + 2¥"(aq) —> X*"(aq) + 2¥6) 87BALANCING EQUATIONS BY INSPECTION Most equations can be balanced simply by inspection. Study the following example. Example 7. Write balanced equations for the following reactions by inspection: (a) Pb;0,—> PbO + On (b) Calli + 0; — CO; + H20 (@) We should begin by considering lead. (Note: We usually balance number of atoms of free elements last.) There are 3 lead atoms on the left hand side but only 1 on the right hand side, To balance number of lead atoms, we must put the coefficient ‘3° before PbO, giving: P30, —> 3Pb0 +0; (nor balanced) before Oz To taunt miter of onypin atoms, we pat“ P0,—> 3P0 +40; (balanced) ‘This is already a balanced equation. Usually, we do not wish any fraction to appear in coefficients, so we multiply all the coefficients by the smallest number (2 here) to give the required answer: 2Pb,04—> 6PLO +O, (balanced) (b) With similar reasoning as in (a), we may proceed as follows CyHio + O;—> 4C02 + H;0 (nor balanced) (To balance number of carbon atoms) CyHip +O; —> 400; + SHO (nor balanced) (to balance amber of hyogen som’) Catto +30, —> 400) + 510 (balanced) Fo balance numberof oxen toms) The required answer is 2CiHyo +130; —+ 8CO, + 10H, 0 (balanced) Note: With more practice, the whole operation can be carried out in one line. 88 MASS AND VOLUME FROM EQUATION Since an equation is a quantitative statement, it is possible to calculate the theoretical quantities of products when the quantities of reactants are Known and vice versa We shall adopt the mole concept in all our calculations. Review the following relationships: 1)_ No, of moles of a substance 2) No. of moles of a gas volume molar volume (at that particular temperature and pressure) In particular, No.of moles ofa gas = olume in dm? (tt) or = Yolume in din? (at room conditions) 24 dm’ 3) No, of moles of solute ae outa = molarity X volume of solution (in dm?) Example 7.6 A recently developed process for reducing the amount of nitrogen oxides in motor car exhaust gases involves the injection of a stream of ‘ammonia gas into the combustion products. The reaction is believed to be: ANHs(g) + 6NO(g) — SNa(e) + 64,0(0) Assuming the average small car emission to be 1.2 g of NO per km travelled, calculate the mass of ammonia needed to react with all the nitrogen’ monoxide emitted by a small car travelling 10 000 km (in one year). Mass of NO emitted = 1.2 X 10000 = 12000 g Molar mass of NO = 30 g No. of moles of NO emitted = TSB. = 1200 - 4oq 89‘As seen from the equation, 4 moles of NH; would react with 6 moles of NO. Necofmnotni, = 400x$ = 267 Molar mass of NH, = 17g Mass of NH; needed = no. of moles X molar mass = 267 X 17 = 4539g Example 7.7 Hydrogen sulphide and chlorine react to form hydrogen chloride and sulphur according to the following equation: H,S{g) + Calg) —> 2HCYg) + S{s) (a) Find mass and volume (at room conditions) of hydrogen chloride formed if (i) 3.4 g of hydrogen sulphide and 7.1 g of chlorine are allowed to react (i) 10.0 g of hydrogen sulphide and 10.0 g of chlorine are allowed to react, (b) At 25°C and 760 mm Hg, 100 cm? of hydrogen sulphide are mixed with 100 cm? of chlorine. Find volume and mass of hydrogen chloride formed (assuming temperature and pressure 10 be unchanged after reaction. fe) In order to obtain 3.2 g of sulphur, what is the minimum volume of chlorine used at 25°C and 760 mm He? (a) At 20°C and 770 mm Hg, 2373 cm of hydrogen sulphide and 781 g of chlorine are mixed. Find mass of hydrogen chloride formed. Molar mass of H,S = 34 g, molar mass of Cl, = 71 g, molar mass of HCl = 36.5 g, molar mass of S = 32 g. (a) (@ No. of moles of = Musing _ 34 (@) © No. of moles of HyS = SME = 34- o10 No. of moles of Ch = 2 = 0.10 90 From the given equation, since H,$ reacts with Cl in a 1:1 ‘molar ratio, therefore both reactants are all used up. Since number of moles of HyS : Cly : HC = 1:1: 2, no. of moles of HCI formed = 0.10 X 2= 0.20 Mass of HCI = 0.20 X 365 = 7.3 g Volume of HCI (at room conditions) = no, of moles X molar volume at room conditions 0.20 X 24.000 = 4800 cm? 100 3a = 0294 100 71 Since 0.141 mole of Cly would react with only 0.141 mole of HS, therefore HyS is in excess. (Cla is called the limiting reagent because it is all used up. Calculations would be based on the amount of limiting reagent only.) From equation, no. of moles of Clz : HCI = 1 = 2, no, of moles of HCI formed = 0.141 X 2 = 0.282 Mass of HCI = 0.282 X 36.5 = 103g Volume of HCI (at room conditions) = 0.282 X 24.000 6768 cm? (W) No. of moles of HS No. of moles of Cl oat (b) From equation, no. of moles of HyS: Cl : HCL = 1 Ratio of volumes of HS : Cl; : HCL= 1: 1:2 100 cm? of Hz$ react with 100 em? of Cl; to produce 200 cm? of HCI at 25°C and 760 mm Hg. No. of moles of HC! = 20 = 0.00833 24 000 Mass of HCI = 0.00833 X 365 = 0.304 g (©) No. of moles of $=32 = 0.10 No. of moles of Cl; required = 0.10 Volume of 0.10 mole of Cl, at 25°C and 760 mm Hg = 0.10 X 24 000 = 2400 cm? @) Let Vz be the volume of HS at s.t.p. Applying the General Gas Equation, 1710 X 2373 _ 760 XV, 293 23 = V, = 2240 cm? 2240 No. of moles of HaS = 3rqqq = 0.10 781 No. of moles of Cl = oll 7 Cy is in excess, and H,S is the limiting reagent. No. of moles of HCI formed = 0.10 X 2 = 0.20 Mass of HCI = 0.20 X 36.5 = 7.3 g Example 7.8 ‘An alcohol P of formula CHy(CH 4OH reacts with sodium metal according to the following equation: 2CH,(CH; nH + 2Na —> 2CHs(CH ONa * Ha When 3.7 g of P is treated with excess sodium, hydrogen gas is liberated which occupies 600 cm* measured at room temperature and pressure. Caleuate the molecular mass of P and hence determine the value of n. volume of gas ‘molar volume of gas aon eeae 24 X 1000 No. of moles of Hz = 0.025 ‘As seen from the given equation, 2 moles of P give 1 mole of Ha, hence no. of moles of P = 0.025 X 2 = 0.050. Since 0.050 mole of P conesponds 103.78, molar mass of P=3.7.X Gao = 74g Hence molecular mass of P = 74 M, of CHs(CH,),OH = 74 ID+1X34(1241X It 16 +1 =74 In = 42 92 Example 7.9 Calculate the volume of oxygen (measured at room conditions) obtainable from 50 cm® of a hydrogen peroxide solution (concentration being 51 g HO per dm° of solution) undergoing the following decomposition: 2H03(aq) —> 2H,0(2) + O2(s) Mass of H,0, in 50 om® of solution = $1 X 7505 = 255 @ Mote mas of 50s = 34 ¢ of meso 03 $0 en? of station = 25 = 075 Sn 7 mols of 0s wal ge I mol of 0, po. of mals of Os ebanable= 0.075 x = 08875 ‘Molar volume of a gas at room conditions = 24 000 em? ‘Volume of O2 obtained = 0.0375 X 24.000 = 900 om* Example 7.10 2A g of magnesium were allowed to react with 200 cm* of 0.80 M hydrochloric acid, What mass of magnesium remained? What volume of ‘gus was evolved at room conditions? Mg(s) + 21C\(aq) —> MeCla(aq) + H3@) Mor ma of Mg = 24 No. of moles of Mg = 24 = 0.10 No. of moles of HCI used = molarity X volume of solution (in dm*) 200 = 0.80 X so 16 0.16 mole of HCI would react with 248 or 0.08 mole of Mg to give 0.08 mole of Ha. No. of moles of Mg remaining = 0.10 - 0.08 = 0.02, Mass of Mg remaining = 0.02 X 24 = 0.48 g Volume of Hy evolved (at room conditions) 0.08 x 24.000 1920 em? 93Example 7.11 (a) Excess copper(il) oxide was warmed with 35.0 om of 1.50 M sulphuric acid until reaction was complete. Calculate the maximum ‘mass of copper(II) sulphateS-water crystals which could be obtained from this solution. (6) What volume of the dilute sulphuric acid in (a) would be required to dissolve 15.9 g of copper(I) oxide? (@) CuO(s) + H,$0, (aq) —> CuSO, (aq) + H,0(8) z 350 No, of moles of H,S0, wed = 150X <5 = 0.0525 Since number of moles of H, SO, no. of moles of CuSO, formed Since CuSO, + SH,0 —*> CuSOs..5H:0, 00525 mole of CuSO, would give 0.0525 mole of CuSO,. 5H30. Molar mass of CuSO,.SH,0 = 249.5 g Maximum mass of CuSO,-SH,0 obtained = 0.0525 X 249.5 = 13.1 g (b) No. of moles of H;S0, required = 0.200 no. of moles molarity = 0.133 dm? Volume of 1,80, required Example 7.12 8.87 g of a solid mixture of sodium chloride and potassium chloride were dissolved in 100 cm? of water. Excess silver nitrate solution was added to the above solution, yielding 19.13 g of silver chloride precipitate. aleulate the percentage by mass of each salt in the original solid mixture, Let mass of NaCl be x g. Then mass of KCI would be (8.87 ~ x) g. Molar mass of NaCI = 58.5 g, molar mass of KCI = 74.5 g We should write separate equations for the reactions NaCl(aq) + AgNO (aq) —> NaNO, (aq) + AgCIG) x za ad 25 Gvantity in motes) 94 KCI(aq) + AgNOs (aq) —+ KNOs(aq) + AgClG) oe 880-4 (quant in ml) Mir mas of AC) = 185g wa, Wo. of mols of Ag fred = $32 « gua2s Bret «ons : x san 388 soon = soot cl by mas = 282x008 = «07% fof KCLby mse = 1006-B.7% = 563% (Note: Provided that all the solution mixture was used in reacting with ‘AgNOs(aq), we do not have to bother about its volume, Thus the value 100 em® does not enter into calculation.) copper(II) sulphate solution in a beaker. After some time, the iron sheet and solid particles in the beaker were carefully removed from the resulting solution, washed with distilled water, dried and weighed. The iron sheet and solid particles together were found to weigh 0.20 g ‘more than the original mass of iron sheet. a} Give the ionic equation for the reaction in the beaker. (b) What would be observed on the surface of the iron sheet? (e) What is the loss in mass of the iron sheet? (a) Fe(s) + Cu?"(aq) —> Fe*(aq) + Cus) (b) Reddish brown coating of copper metal (©) In the reaction, some iron is replaced by copper metal. From equation, for 1 mole of Fe(56 g) lost, 1 mole of Cu(63.5 g) will be formed. It follows that for 56 g of Fe lost, net increase in total mass of solid = 63.5 — 56 Los in mas ofthe ron sheet = 56x 222 = 15g 188 95Example 7.14 When 5.0 g of a mtcture of sodium carbonate (anhydrous), sodium hydrogen carbonate and sodium chloride (a) is heated until there is no further reaction, 200 cm* of carbon dioxide measured at sp. are collected (b) is treated with excess dilute hydrochloric acid, 928.2 cm? of carbon dioxide measured at .t,p.are collected, Calculate the composition. of the mixture in g. (HKCEE) (@) On heating, only NaHCO, decomposes. NaHCO, (s) —> NayCO,(s) + Hs0(®) + CO3(@) No. of moles of CO; = 0.00893 200 22400 No. of moles of NaHCO, = 0.00893 X 2 = 0.01786 Molar mass of NaHCO, = 84g Mass of NaHCO; 0.01786 x 84= 15g (b) NaHCO, and NaCOs both react with HCI to give CO3, while NaCl does not. NaHCO,(s) + HCl(aq) —> NaCl(aq) + Hz O(@) + CO,(g) asC03(6) + 2HCI(aq) —+ 2NaCl(aq) + HO) + COs() No. of moles of CO; 0.01786 mole of NaHCO; will give 0.01786 mole of CO, No. of moles of CO, formed from Na,CO, = 0.04144 ~ 0.01786 = 0.02358 No. of moles of NazCO, = 0.02358 Molar mass of NazCO3 = 106 g Mass of NayCO; = 0.02358 X 106 = 25g Mass of NaCl = 50-15-25 = 10g Sometimes, a series of reactions may be involved in changing a reactant into the final desired product. For the sake of simplicity in calculations, we may omit the intermediate steps and write a simplified ‘equation’ which involves only the reactant and the final product. ‘The aforesaid is best illustrated by the following example Example 7.15 The following experiment was performed in a school laboratory: 100 g of copper were completely dissolved in excess concentrated nitric ‘acid, The mixture was heated to dryness to give copper(II) nitrate, which ‘on strong heating, gave copper(II) oxide. The copper(II) oxide was dissolved in hydrochloric acid to give a solution of copper(il) chloride, which was reduced by Fehling's solution to give a precipitate of copper(I) oxide, (a) Find the theoretical mass of copper(I) oxide obtained by the experiment. (5) Would you expect the actual mass of copper) oxide obtained to be equal to the theoretical yield? (@) The whole process may be represented by a sequence of steps: 0 tea ue. reduction cu cup) => uo “+ cua, "+ cu,0 and for the overall reaction, 2Cu —+ Cus0 (the “2 before Cu is added to balance no. of Cu atoms) Thus 2 moles of Cu would give 1 mole of Cu30. Molar mass of Cu = 635 g, molar mass of Cu;0 100. No. of moles of Cu used = 292. = 1.57 143 g 0.785 No. of moles of Cu,0 formed = “3~ ‘Theoretical mass of Cuz0 formed = 0.785 X 143 = 112 g Note: In the above method, we can save the trouble of finding masses of the intermediate products (i. Cu(NOs)s, CuO and CuCl). (b) The actual mass of CuzO obtained would be smaller than the theoretical mass, as there was loss of material in each step due to limitations of the experimental techniques. 7EXERCISE 7 FINDING EQUATION FROM EXPERIMENT 1) 0.24 g of a metal M (atomic mass = 24) was dissolved in excess hydrochloric acid (HCI), 240 cm? of hydrogen (H,) being collected at room conditions. Another product formed is MCls. Write an equation consistent with the given information, 2) 2.48 g of an element Z (atomic mass = 31) burnt in oxygen (O2) to produce 5.68 g of oxide. Write an equation for the reaction. 3) 12.5 cm? of 0.10 M sulphuric acid (H,SOs) were needed to react completely with 25.0 cm? of 0.10 M sodium hydroxide (NaOH) solution to give sodium sulphate (Nay$O,)) and water. Deduce (a) an equation (b) an ionic equation for the reaction 4) A piece of copper (mass = 24.58 g) was immersed in aqueous silver nitrate solution in a beaker. A silvery deposit of crystalline silver ‘was seen to form on the copper surface and the solution gradually tumed blue. The beaker was allowed to stand overnight. The silver deposit was carefully removed, washed with distilled water and dried, and found to weigh 1.94. ‘The final mass of remaining copper was 24.01 g (@) Why id the solution gradually turn blue? (©) What mass of copper reacted with silver nitrate? (©) How many moles of copper reacted? (@) How many moles of silver were formed? (©) Find number of mole of silver metal produced when one mole of copper(I!) ions is formed. (8) Write anionic equation forthe reaction. 5) It was found that 20.0 cm? of 1.0 M hydrochloric acid (HCI) were required to neutralize 200 cm? of 0.50 M sodium carbonate (NazCOs) solution. In a second experiment, 0.318 g of anhydrous sodium carbonate was treated with excess hydrochloric acid and 673 em? of carbon dioxide (at st.p.) were collected. Deduce an ionic equation representing the reaction between sodium carbonate and hydrochloric acid. 6) Molar solutions of lead) nitrate and potasium iodide were mixed (in test tubes of equal bores) in volumes shown in the following table. A yellow precipitate (Pbl,) was formed in each case and all tubes ‘were centrifuged for the same length of time. The heights of the 98 precipitate were measured and recorded below: Volume of LOM PHINOs!2 (om) | 5 | 5 |S | § | § | 5 | 5 |S Volume of 1.0M rp 4] 6] 8 io fiz fas fae fis Height of poe. s}o7]10 12/12 ]i3 |r formed (em) ° il el el eel el Plot a graph of ‘height of precipitate” against ‘volume of 1.0 M KT’ Deduce an ionic equation for the reaction. 7) (@) Molar aqueous solutions of barium chloride (BaCls) and a metal sulphate of molar mass 342 g were prepared. (@ What mass of anhydrous barium chloride would be needed to prepare 250 em? of a molar solution? ’) A white precipitate was formed when the two solutions were mixed. What is this white precipitate? (b) The two solutions mentioned in (a) were mixed in six identical tubes in volumes shown in the following table. A white precipitate was formed in each case and it was allowed to settle for an hour and its height was then measured. Test tube 4 [elelple lr Volume of M BaCl, (em?) 10| 20] 30] 40| 50| 60 Volume of M metal sulphate (en? )| 10] 10| 10| 10] 10] 10 Height of ppt. formed(em) _[os|t.ojis|is|is|is (i Why id the height of precipitate stay constant in tubes CD,£and FP (ii) What volume of barium chloride solution reacted just completely with 10 cm? of the sulphate solution? (ii) How many moles of barium chloride would react with one mole of the metal sulphate? How many moles of sulphate jons are contained in one mole of the metal sulphate? Gv) If each mole of metal sulphate contains two moles of metal jon, write the formula for the metal sulphate using the symbol M for the metal. (¥) Caleulate the atomic mass of the metal M. 99(vi) Write an equation for the reaction. (vil) Write an ionic equation for the reaction. BALANCING EQUATIONS BY INSPECTION 8) Balance the following by inspection: (@ H, +0,— #0 (0) NHy + 0;— NO + H,0 (©) CaHy + 0,—> CO, + H,0 (@) CuO + NH) —> Cu +N; + H,0 (©) Alls) + Fe*(aq) —> Al'“(aq) + Fe(s) MASSES AND VOLUMES FROM EQUATIONS 9) From the equation, AF eS; (3) + 1102 (g) —> 2Fe203(s) + 8502(g) calculate (@) the volume of sulphur dioxide, measured at 25°C and 1 atmosphere, that would be obtained by the complete oxidation of 100 g of iron pyrites (FeS2) (b) the volume of air, measured at 25°C and 1 atmosphere, used in the above oxidation, assuming that air contains 20% oxygen by volume. 10) 2.64 g of ammonium sulphate were heated with excess calcium hydroxide and the following reaction occurred: (NH)2804(3) + Ca(OH)s(s) —> CaS04(6) + 2NH,(@) + 2H;0(@) The ammonia formed was passed over excess heated copper(II) oxide. 3CuO() + 2NH3(g)—> 3Cu(s) + Na(g) + 3H,0(2) Assuming all the ammonia to have reacted, calculate (a) mass of copper formed (b) volume of nitrogen produced at room conditions. 11) On heating 12.25 g of KCIO; for 2 minutes, there is a weight loss of 0.968. 2KC103(5) — 2KCI) + 302(8) What percentage by mass of the original KCIO, has decomposed? 12) Calculate the mass of mercury(II) oxide which will give as much ‘oxygen a8 10 g of potassium chlorate on thermal decomposition. 2HHg0(6) —+ 2Hig(2) + 0216) 2KCI05(s) — 2KCKG) + 30316) 13) When magnesium powder is heated strongly in a current of nitrogen, 4 yellow solid magnesium nitride (MgyNa) is formed. On treatment with water, this solid gives ammonia and magnesium oxide. (@) Write an equation for the formation of magnesium nitride, (b) Write an equation for the action of water on magnesium nitride. (©) Find mass of magnesium nitride which could be obtained from 10.00 g of magnesium. (@) If the amount of magnesium nitride obtained in (c) is boiled with excess water, find (i) mass of magnesium oxide (ii) volume of ammonia produced, measured at 25°C and 760 mm Hg. 14) 7.15 g of hydrated sodium carbonate (NazCO,.nH,0) were treated with excess nitric acid to produce 600 em? of carbon dioxide measured at room conditions. Calculate the value of n. 15) A metal nitrate X0NO,); decomposes on heating according to the following equation: 2X(NOs (3) —+ 2X06) + 4NOs(G) + Os(a) If 378 g of the metal nitrate yield 11.2 dm? of gases (reduced to s.t_.) on complete decomposition, calculate (@) the total number of moles of gases evolved (b) the number of moles of metal nitrate decomposed (©) the formula mass of metal nitrate (@) the atomic mass of metal X. 16) 6.000 g of a solid mixture of magnesium carbonate and calcium carbonate gave 1448 cm? of carbon dioxide (corrected to s.t.p.) when completely decomposed by strong heating, Find mass of ‘magnesium carbonate in the mixture. 17) 1008 g of a solid mixture of anhydrous sodium carbonate and sodium hydrogen carbonate heated at a moderate temperature gave 1 constant mass residue of 8.22 g. Calculate the percentage by mass of anhydrous sodium carbonate in the mixture. What mass of carbon dioxide is formed when 2.00 g of the same mixture is treated with excess dilute nitric acid? 18) A sulphur-containing ore was treated with strong oxidizing agent to convert all sulphur to sulphate, The excess oxidizing agent was removed and the sulphate was precipitated as barium sulphate and 101weighed. What is the percentage by mass of sulphur in the ore, 100 g of which yielding 55.6 g barium sulphate? 19) A specimen of iron ore was found to contain 36% of haematite (Fez0s) and 20% of silica (SiOz) by mass. If 1000 kg of this ore are placed in a blast furnace and reacted, calculate (a) the mass of iron which will be produced (b) the mass of limestone needed to ‘tum all the silica into slag (CaSiO3 ). (AKCEE) Hint: CaCO4(s) —> CaO{s) + CO3(@); limestone Ca0(5) + Si02(3) — CaSi03(6)_) 20) 12.5 g of limestone are treated with excess dilute hydrochloric acid. The gas evolved is completely dissolved in a solution of sodium hydroxide whose mass is thereby increased by 5.1 g. Give equations for the reactions that take place and calculate the percentage of calcium carbonate contained in the limestone. (HKCEE) 21) Sodium nitrate decomposes on heating according to the following equation: ‘2NaNO;(s) —> 2NaNO, (5) + O2(g) A sample of sodium nitrate contains some sodium chloride as impurity On strong heating, 8.50 g of the sample left a residue of 7.10 g. Calculate the percentage by mass of sodium nitrate in the sample 22) When a sample of lead(II) carbonate is heated, a gas is evolved and. collected. On completion of the reaction, the yellow residue formed is found to weigh 6.69 g. What is the volume of the gas if measured dry at st.p.? Half of the yellow residue by mass is heated strongly, and a current of town gas is passed over it until there is no further reaction. Calculate the mass of the lead formed. The other half of the yellow residue is dissolved in excess of dilute ethanoic acid (acetic acid). What is the maximum mass of lead(II) ethanoate (acetate) trihydrate which can be obtained from the solution? (HKCEE) (Hint: PLCOs(s) — POG) + CO2(8); yellow residue PbO(S) + Ha(g) —> Pb(s) + H20(); PbO(s) + CO(g) —> Pb{s) + CO2(e); PbO(S) + 2CHsCOOH(aq) —> (CH; COO): Pb(aq) + H20(@); 102 (CHCO0):Pb + 3H;0 —*+ (CH;COO).Pb.3H,0 lead(D)ethanoate wiydrate +) 23) In the presence of a catalyst, sulphur dioxide reacts with oxygen according to the following equation 2802(g) + O2() —* 2803(8) (@) Given that all measurements are made at the same temperature and pressure, (@) what volume of oxygen is needed for the complete oxidation of 200 cm? of sulphur dioxide? Gi) what volume of sulphur trioxide will be produced? (6) How many moles of pure sulphuric acid can be made from 200 cm? of sulphur dioxide measured at stp. by the above method? (HKCEE) 24) The maximum mass of copper(It) sulphate crystals CuSO, SH:0 oblainable from 200 g of a sample of brass (containing only zinc and copper) is 37.2 g. What mass of zinc is present in 20.0 g of the sample of brass? 25) 100 em? of a solution of copper({l) sulphate are diluted with distilled water to 500 cm®. An excess of sodium hydroxide solution is added to 100 cm? of the diluted solution. The precipitate formed is filtered off, washed and finally heated strongly to give 1.20 g of a black residue. (a) Write equations forall the reactions mentioned. (b) What is the molarity of the diluted copper(t1) sulphate solution? (©) How many moles of copper(II) ions are there in 300 em? of the diluted solution? (@) Calculate the concentration of the original solution in. grams of CuSOs SHO per dm? (©) If 25.0 cm® of the original solution are treated with an excess of barium chloride solution, what is ()) the maximum number of moles and (i) the maximum mass of barium sulphate precipitate obtainable? 26) A piece of iron containing carbon as the main impurity weighs 4.0 g and is allowed to react with dilute hydrochloric acid until no further reaction. Then the mixture is filtered and washed. The filtrate, 103together with the washings, is slowly treated with sufficient con- centrated nitric acid until! no further change, and then excess ammonium hydroxide is added. The resulting precipitate is filtered off, washed, dried and finally heated to redness until the mass is constant, The mass of the produet is found to be $ g. (2) Calculate the percentage of iron by mass in the original piece. (b) Describe the reactions involved and give equations where appropriate. (HKCEE) 104 8 VOLUME ANALYSIS IN GASEOUS REACTIONS GAY LUSSAC’S LAW AND AVOGADRO'S LAW Having studied the results of a large number of reactions involving gases, a scientist called Gay Lussac noticed that volumes of gases (measured at the same temperature and pressure) bore simple ratios. For example, when hydrogen and oxygen combine, 2 volumes of hydrogen + 1 volume of oxygen —> 2 volumes of steam and for the reaction between hydrogen and chlorine, 1 volume of hydrogen + 1 volume of chlorine —+ 2 volumes of hydrogen chloride He expressed his findings im what is now known as Gay Lussac’s Law of Combining Volumes: When gases react, they do so in volumes which bear a simple ratio to one another, and to the volumes of the products if gaseous, all volumes being measured under the same conditions of temperature and pressure. Another law, Avogadro’s Law, can be used to explain Gay Lussac’s Law. Avogadro's Law states that equal volumes of all gases, under the same conditions of temperature and pressure, contain same number of molecules. This law enables us to tun volume ratio into mole ratio, and vice versa, in gaseous reactions. For example, in the combination of hhydrogen and chlorine to form hydrogen chloride, the reaction is represented by Th) + Ca) — 2HC1@) 1 mole 1 mole 2 moles. or 1 molecule 1 molecule 2 molecules 1 volume 1 volume 2 volumes J} trom equation (By Avogadro's Law) The ratio of volumes of Hy : Cly : HCI= 1: 1: 2 (a simple ratio) 10sSince for other gaseous reactions, stoichiometric coefficients (or mole ratios) of reactants and products are expected to be small whole numbers, volume ratios should also be in simple ratios. Gay Lussac’s Law can thus be explained. Gay Lussae’s Law and Avogadro's Law find applications in calculating gaseous volumes in chemical reactions, Example 8.1 Calculate the volume of oxygen required for complete combustion of 100 cm? of propane, What is the volume of carbon dioxide formed, ‘assuming all volumes to be measured at room temperature and pressure? Write the balanced equation for the reaction frst. C)He(g) + 502(@) —> 3C03() + 44,00) Imole 5 moles 3 moles (from equation) I volume 5 volumes 3 volumes (by Avogadro's Law) 100 em? ’ 1 By simple proportion, volume of Oz required = 100 X 5 cm? = 500 em? volume of CO; formed = 100 X 3 em? = 300 om? Example 8.2 What volume of oxygen will be required to burn completely a mixture of 100 cm? of methane, 200 om? of hydrogen and 250 cm? of carbon monoxide, all volumes of gases being measured under the same conditions of temperature and pressure? Equations for the rections: CHG) + 203(¢) —— COr() + 2H,0(@) 2H (g) + O22) —— 2H:0@) 2CO(g) + O2(g) ——+ 2C03(g) The total volume of O, required = volume of 0, for combustion of CH, + that for Hy + that for CO = 100 x 2+ 200 x4 250 x b= 200+ 100 + 125 = 825 em! 106 Example 83 500 cm? of hydrogen (volume corrected to stp.) are burnt in excess chlorine. What is the volume of hydrogen chloride produced at 25°C and 750 mm Hg pressure? Equation for the reaction H,(@) + Ch(@) — 2HC1@) 1 molecule 2 molecules (from equation) 1 volume 2 volumes (by Avogadro's Law) 500 em? 1 ‘Volume of HCI produced at sp. = 500X2 = 1000 em? Applying the General Gas Equation, volume of HCI at 25°C and 750 mm Hg M3428 , 160 1000 x “S73 * 730 1106 cm? Example 8.4 A solid element X (atomic mass = 32) burns in excess oxygen to form a gaseous oxide Y. The volume of gas after combustion is equal to that before combustion provided both volumes are measured under the same conditions of temperature and pressure. The molecular mass of ¥ is 64, (a) How many atoms of oxygen are there in one molecule of Y? (b) Write the formula of Y. (ec) Write the equation for the reaction, (@) In reacting with element X, 1 volume of Oz (g) gives 1 volume of ¥@). 1 mole of Oa(g) gives 1 mole of Y(g) (by Avogadro's Law). In other words, 1 mole of ¥ contains 2 moles of oxygen atoms. 1 molecule of ¥ contains 2 oxygen atoms. (b) Given M, of ¥ is 64. Let formula of ¥ be XnO2, where n 32n +16 X 2 = 64; n= 1; Yis X03. (©) Equation X(s) + O2(8) —> X02(g) in integer, 107COMPOSITION OF GASEOUS MIXTURES To find composition of a gaseous mixture, the mixture is usually allowed to react with oxygen or some other gases and the volumes of gaseous products are then measured. There may be expansion or contraction as evident from the equation, The residual mixture of gases is usually treated with various reagents in turn, each capable of absorbing a particular 125, s0 that the contraction in volume on treatment with a certain reagent gives the volume of the gas having been absorbed by it. The following points should be noted: (1) Hydrocarbons (compounds containing carbon and hydrogen only) and organic compounds containing only carbon, hydrogen and oxygen ‘burn in air or oxygen to form carbon dioxide and water as the only combustion products. 2) On sparking a mixture of hydrogen and air, hydrogen and oxygen combine to form water, but there is very little reaction between hydrogen and nitrogen, or between oxygen and nitrogen. So we can assume the only reaction which takes place is formation of water () Liquid water has negligible volume when compared with gaseous volumes. Therefore in reactions giving water as one of the products, the final volume depends very much on whether the water exists in vapour or liquid state ‘Take the example of combustion of propane (CsHs): ( Suppose all volumes are measured at 115°C and 750 mm Hg, CaHe(G) + 503(@) —> 3C03(g) + 442 0) L molecule $ molecules 3 molecules 4 molecules (from equation) I volume 5 volumes 3 volumes 4 volumes (by Avogadro's Law) Expansion in volume = (3 + 4) — (1 + 5) volume = 1 volume Wore: The given temperature 115°C indicates that the water formed exists in gaseous state; the exact temperature, as long as it is above the boiling point of water, whether 115°C or 215°C, does not alter the above calculation provided all volumes are measured under the same conditions of temperature and Pressure.) Upon cooling the above residual mixture to temperatures below the boiling point of water, there will be a contraction of 108 approximately 4 volumes due to condensation of steam. (The contraction is not exactly 4 volumes because on cooling, carbon dioxide will also contract, though to a much lesser extent — the contraction can be calculated using the General Gas Equation.) Gi) fall volumes are measured at 30°C and 750 mim Hg, C3Ha(g) + 502(8) —+ 3C0,(g) + 4H,0(2) L volume 5 volumes 3 volumes negligible volume Contraction in volume = (1 +5)— (3 +0) = 3 volumes (@) Carbon dioxide is absorbed by concentrated aqueous solution of potassium hydroxide (caustic potash) or sodium hydroxide (caustic soda). But when aqueous calcium hydroxide (ime water) is used, the action is slower. The contraction in volume on treatment with alkali solution therefore gives the volume of carbon dioxide present. (5) Oxygen is absorbed by an alkaline solution of pyrogallol. (©) Carbon monoxide is absorbed by ammoniacal copper({) chloride solution. (7) Hydrogen is absorbed by palladium (@ metal) (B) Water apour i absorbed by ding agents e.concentrated sulphuric acid. (©) Volume of s mixture of gus may depend on solubility ns particular solvent. For example, a mixture of 20 em? of NH and 30 cm? of Nz has & total volume of (20 + 30) = 50 cm?; after shaking with some water, all the NH dissolves and the volume becomes 30 em?. Examples of very soluble gases are: NH, HCl, SO, ete. Example 85 100 cr? of hydrogen were exploded with 160 cm® of oxygen. What is the finel volume if all volumes were measured at (a) 110°C and 1 atmosphere (b) 25°C and 1 atmosphere? @ 2G) + O@) — 21,06) 2 moles 1 mole 2 moles (from equation) 2 volumes 1 volume 2 volumes (by Avogadro's Law) 10cm? + 50 cm* 100 em? 109Volume of unreacted 0; = 160 ~ 50 = 110 em* Final volume = volume of unreacted 0; + volume of steam formed = 110+ 100 = 210 cm? (b) 2H2(8) + 028) —> 2H, 0(8) 2 volumes 1 volume volume of liquid water negligible 100 cm? ‘ 50 cm? Final volume = volume of unreacted 0, = 110 em? In problems involving a mixture of gases, we can use x, ¥,Z,....t0 represent volumes of various components. Volumes of other gaseous reactants and products may then be expressed in terms of x, ¥, 2%... as can be deduced from the chemical equations concerned. By equating ‘these algebraic terms to numerical figures (from the given data) and solving the equations, x, y, 2, .... and thus composition by volume of the mixture can be found. Example 8.6 250 em? of a mixture of ozone and oxygen measured at 30°C and 760 mm Hg are converted into oxygen by heating. If the total gaseous volume after heating is found to be 300 cm? measured at 35°C and 752 mm Hg, what is the percentage by volume of ozone in the mixture? Lot the volume of ozone in the original mixture be x em? Since the initial and final volumes are measured under different conditions of temperature and pressure, so before volumes are compared, they should be adjusted to correspond to the same temperature and pressure. ‘The final volume of gus after heating if measured at 30°C and 273 + 30, 752 x BE = 292 om? 760 mm Hg = 300 x S732 x 7% ‘The increase in volume = 292 — 250 = 42 cm® which is due to the following reaction 203 (g) —> 30,(8) 2volumes 3 volumes xem? 3x om? 2 10 Increase in volume Putting 5 = 42; x = 84cm? The % volume of ozone in the mixture = 355 X 100% = 33.6% 251 Example 8.7 24 on? of a mixture of ethene (C,H), ethyne (CoH) and nitrogen were exploded with 60 em of oxygen. The resulting mixture of gases ‘was reduced in volume by 40 om? on shaking with potassium hydroxide solution; another reduction of 6 em? was observed on shaking with alkaline pyrogallol solution. Find the composition by volume of the ssiven. mixture, assuming that all volumes are measured under room conditions volume of gas absorbed by alkaline pyrogallol Volume of O; remaining unreacted Volume of 3 reacted Volume of CO; produced volume of gas absorbed by KOH = 40 cm? Let the volumes of ethene and ethyne be x em? and y cm? respectively. CaH4(g) + 302(g) —> 2CO,(g) + 2H,0(8) Volume inem’ x 3x 2 . 2CaHa(e) + 503 @) — 400468) + 2H, 02) ' Volume inem ys Sy ay 7 H 5 i Equating volume of O, :3x+Sy = 540-22. O Equating volume of CO; : 2x + 2y = 4 ‘i Solving equations (i) and (ii), we get x = 8, y = 12 8 cm?, volume of ethyne = 12 cm?, 4-8 12= 4m? a) ‘Volume of ethen volume of nitrogen unExample 8.8 55 em* of a mixture of nitrogen, carbon monoxide and hydrogen were burnt in 20 om? (an excess) of oxygen. The final volume after cooling was 50 cm? and of this 20 cm? were absorbed by sodium hydroxide solution. Find the composition of the original mixture. (Assume all volumes were measured at room temperature and pressure.) Let x em? and y em? be the volumes of CO and H, respectively. Nz does not burn in oxygen. Equation for combustion of CO: 2CO(@) + One) —> 2C0,6) 2 volumes 1 volume 2 volumes xem? Zen? xem? volume of C0, fomed volume of gas absorbed by NaOH solution 20 cm? Volume of CO (x em?) x 2 = X om? | Decrease in volume = (x +> — x) em? = 3 =O. ° P= 10 om’ Equation for combustion of Hy 2H3(g) + 02(g) ——> 2H,0(8) volumes olin — yer Let = = +L jem = Yom Decrease in whine = (y +2) on? = 2 Total decrease in volume = 55 +20 — 50 = 25 em* y= 10 Hence the original mixture contains 20 em? of CO, 10 cm? of Hz and 55 — 20 ~ 10 = 25 cm? of Na 2 MOLECULAR MASS AND GAS DENSITY Molar mass of a gas may be calculated from its density by the following steps: (1) Find density of the gas at s.t-p. in g dm’ from the given data (2) Multiply the density at s.tp, by 22.4 to find the mass of one mole of the gis, ie. its molar mass. (Note: If density of gas at room temperature and pressure is given or found, multiply by 24 in Step 2 instead.) Example 8.9 The density of a gas at 27°C and 780 mm Hg is 4.67 ¢ dm. Caleulate its molar mass, 273 +27 aor x 2 5.00 g dm? (ote: The above calculation involves reasoning by simple proportion if temperature is lower, volume will be smaller, therefore density higher; if pressure is smaller, volume will be bigger, therefore density lower.) Density of the gas at s.t-p, Molar mass of the gas = density X molar volume (both at s.tp.) 500X224 = 112g It is also possible to calculate the molecular mass of a gas if its vapour density is known, By definition, vapour density of a gas = = mass of a given volume of the gas ‘mass of the same volume of hydrogen at the same temperature and pressure (Note: The densities or masses concerned must carry the same unit.) If the volume of gas is chosen to be 22.4 dm? at s.t.p., molecular mass of the gas ‘molecular mass of hydrogen Molecular mass of hydrogen (H) is 2 on carbon-12 scale Molecular mass of gas = vapour density of gas X 2 vapour density of a gas = 413For example, the molecular masses of helium, oxygen and carbon dioxide are 4, 32 and 44 respectively, therefore their vapour densities are 2, 16 and 22 respectively. Note: 1. Vapour density is a ratio; it caries no unit. 2. Vapour density can also be defined for the vapour of a volatile liquid or solid. 3. The vapour density of air is approximately 14.4; thus a gas is denser than air if its vapour density is greater than 14.4, e.g. COs (vapour density = 22) is about 1.5 times as dense as air. Example 8.10 From the following data, calculate the molecular mass of gas A. Mass of evacuated flask = 100.10 g ‘Mass of flask + hydrogen = 100.24 g Mass of flask + gas A= 107.94 g (Temperature and pressure of all gases are measured at room conditions) ‘mass of a given volume of gas A ‘mass of the same volume of Hy 107.94 — 100.10 100.24 — 100.10 M, of gas A = 56X2 = 112 Vapour density of A = 56 Example 8.11 A certain volume of a gas B has a mass of 0.34 ¢ while the same volume of nitrogen has a mass of 0.28 g, both measured at 25°C and 760 mm Hg. What is the molecular mass of the gas? Vapour density of gas B density of gas B ‘density of Hy density of gas B density of Nz density of Nz ~ density of Hy = Mass of a given volume of BB y savour density of Ne ‘mass of same volume of Nz mass of a given volume of gas By Mr of No “tas of same volume of Ny <2 14 = 4 28 0.28 2 =u My of gas B = vapour density of gas B X 2 = 17X2 = 34 MOLECULAR FORMULAE FROM GAS ANALYSIS Molecular formulae of gases and volatile liquids can often be found by gas analysis. Study the following examples. Example 8.12 A gaseous oxide of chlorine, Cl, Oy, decomposes on heating 2A Oy() —> xCla(¢) + ¥O2(8) 30 cm? of the oxide gave 30 cm? of chlorine and 15 cm? of oxygen {all volumes being measured at room temperature and pressure). Find the formula of this oxide. 2€1,0,(@) —> xCl(g) + yOre) 2 moles x moles —_y moles (from equation) 2 volumes x volumes y volumes (by Avogadro's Law) 30 cm? 30cm? 15 cm® (given data) Since 30 cm? correspond to 2 volumes, 15 em* must correspond to 1 volume. xe2yel Formula of the oxide = CO Example 8.13 10 cm? of a gas Yq were heated, forming 15 om of another gas Y, as the only product. Find the value of n, assuming that all volumes were measured at the same temperature and pressure, (Y is not an atomic symbol ~ it just denotes an element.) Equation for the reaction: 2Ya(g) — 2¥2@) 2 volumes n volumes. (from equation) 10 cm 15cm? (given data) usas 0 Bowie 1 ee) Example 8.14 30 em? of a gaseous oxide AO, react with 15 cm* of oxygen to form 30 em? of another gaseous oxide of element A. Find the molecular formula of the product. Let the molecular formula of the product be AxOy, where x and y are integers. Given: 30 em? of AO; + 15 cm? of 0; —+ 30 cm? of AxOy ie, 2 volumes of AO; + 1 volume of 0; —+ 2 volumes of AxOy By Avogadro's Law, mole ratio of AO; : Op : Ay, =2: 1:2 The balanced equation for the rection is: 2AOs(8) + O38) — 24,0y(8) It follows that x = 1, y = 3 Molecular formula of the product is AOs. Example 8.15 30 cm* of a gaseous compound G, on complete decomposition, save 60 cm? of a mixture of nitrogen and hydrogen. The mixture was exploded with 30 cm? of oxygen. After cooling, the volume of residual gas was 22.5. cm’ (a) Find the composition of the mixture. (6) Determine the molecular formula of compound G. (AUl volumes were measured at ron: temperature and pressure.) (@) Nz has no reaction with O, Equation for the feaction between H; and O; 2H, (8) + O2(g) —> 2H, 0(@) 2 volumes 1 volume negligible ———— volume 3 volumes By Avogadro's Law, 2 volumes of Hz react with 1 volume of Oz Since the decrease in volume is equal to the total volume of Hy and 0; reacted, it follows that: 116 Volume of Hz in the mixture = 2X decrease in volume 5 (60+ 30 ~ 22.5) em? = 45 cm? Hence volume of nitrogen in the mixture = 60 — 45 = 15 cm? (©) From (a), 30 em? of compound G —+ 15 em® of nitrogen + 45 cm? of hydrogen — 1 volume of nitrogen +3 volumes of hydrogen or 2 volumes of G or 2 molecules of G — | molecule of nitrogen +3 molecules of hydrogen Let the molecular formula of compound G be NxHy. 2NyHy—> Nz + 3H, (ince nitrogen and hydrogen are diatomic) Thus x=1y=3 Hence the molecular formula of compound G is NHs Molecular formulae of simple gaseous organic compounds If the molecular formula of an organic compound is not known, letters can be assigned (o represent the number of different atoms present. ‘These numbers may sometimes be found by burning the compound in ‘oxygen and analysing the volumes of gaseous reactants and products. In using this method, a balanced chemical equation has to be written to represent the combustion reaction, ation for complete combustion of a hydrocarbon of formula Cally +¥)0, — xco, +¥ Cally + («+4 )0, —+ xC0, +2 H,0 Equation for complete combustion of an organic compound of formula. CxHyOg +@+%~2)0,— x CxHyO, + & +4 -Z)0, —+ x0, +4 120 Study the following examples, | 7Example 8.16 60 om? of oxygen were added to 10 cm? of a gaseous hydrocarbon. ‘After explosion and cooling, the gases occupied 50 cm*, and, after ‘absorption by potassium hydroxide solution, 30 cm? of oxygen remained. Calculate the molecular formula of the hydrocarbon, assuming all volumes to be measired at room conditions. Let the molecular formula of the hydrocarbon be CxHy. From the given data, volume of CxHy reacted = 10 cm? volume of 03 used up = 60 ~ 30 = 30 em? volume of CO; formed = 50 ~ 30 = 20 cm* ‘The equation of reaction: CaHiy@) + (& +£)03(@) — x€Or() + F100) 1 volume (+2) volumes x volumes 10cm* 30 cm! 20 cm? volume of CO, _ x _ 20 . volume of Hy T ~ 10 Similaly, _&tD _ 30 volume of O; = 2 e Folume of Cy = —T TOR ea oe ‘Molecular formula of the hydrocarbon is C2 Ha Example 8.17 0.60 g of @ gaseous hydrocarbon E when completely burnt in oxygen gave 1.76 g of carbon dioxide. (a) Find the empirical formula of E. (b) E required 3.5 times its own volume of oxygen (measured at the same temperature and pressure) for complete combustion. Find the ‘molecular formula of E: fc) Calculate volume of carbon dioxide produced when a mixture of 35 cm? of E and 35 em® of oxygen is sparked, (All volumes are ‘measured at 18°C and 1 atmosphere.) 118 @ ©) © 12, a Since all the C in CO; came from the hydrocarbon £, Fraction by mass of C in CO; mass of C in 0.60 g of £ = 1.76 X 048 g 44 Mass of hydrogen = 0.60 — 0.48 = 0.12 g Carbon | Hydrogen Relative masses (in g) 0.48) O12 Relative no. of moles of atoms 0.48, -oo | 22-012 (aivide by the smallest no.) Empirical formula of £ is CHs Let the molecular formula of F be (CHs)q of CqHsq, where n is an integer. Since CyHy(g) + (« +4) 03 @) —> xCOx(@) + % H0(8), the equation for combustion of £ would be: CaHlan(e) + (0 +22 )Oa(@) — nCOr@) + 2 H:00) 3n 1 volume (a + 22) volumes Since E required 3.5 times its own volume of Oz for complete combustion, Molecular formula of £ is CH, 2CzHs(@) + 702(8) ——r 4CO2(@)_ + 6H20(0) 2volumes 7 volumes 4 volumes — CaHe is in excess and thus 3 is the limiting reagent. ngVolume of C04 produced = vohine of 0, x $ aoe 35 x5 om 20 em? Example 8.18 12 em? of a gaseous hydrocarbon were sparked with excess oxygen and @ contruction of 24 em was observed. A further contraction of 24 cm? occurred on absorption with sodium hydroxide solution. If all volumes were measured under room conditions, what is the molecular formula of the hydrocarbon? Let molecular formula of the hydrocarbon be CxHy: 12 em’, From given data, volume of CxHy reacted 24 om? volume of CO; formed Cably(e) + (x +4) Oa(e) — xCO.G) + 5 1,00) volume (x+%) volumes x volumes — I volume (c+) vo 7 tom 24.om* Ro M wee? 17a ‘The contraction after reaction (before treatment with NaOH) = (1x42) — x volumes = (1 +%) volumes (txt) — xv0h (+4) yok 14d contraction in volume 4 volume of CxHy 24 mie y Molecular formula of the hydrocarbon is C>Ha. Example 8.19 34 cm® of a gaseous organic compound containing only carbon, hydrogen and oxygen required 136 cm of oxygen for complete com: bustion. The volumes of carbon dioxide and steam formed were 102 m* each, Find the molecular formula of the organic compound if all volumes were measured at 110°C and 760 mm Hg. 120 Let the molecular formula of the compound be C,Hy O,, From given data, volume of CxHyO, reacted = 34 cm* volume of O2 used = 136 om? volume of CO; forme: volume of steam formed CHy Orla) + (x + — F) Oa) —> xCOrGe) + ¥_ 2) volumes x volumes % volumes Trolume (x +¥ — F)voh umes % vol Bdem? ——136em? 102m? 102 em? volume of COp__ x _ 102 A woume of CHyO, ~~ 34 x wlumeofsteam 3 102. yy ag voume of CHO, 1" 34 + °¥ x +d volume of, & 75 136 = volume of C,HyO, eee Molecular formula of the compound is C;H,0. EXERCISE 8 AVOGADRO'S LAW AND COMPOSITION OF GASEOUS MIXTURES 1) In each of the following reactions, volume of one of the involved gases 5 given, Calculate volumes ‘of other gaseous seactants and products. (All volumes are measured at the same temperature and pressure) (@) 2NO@) + 036) —> 2NOs(@) 20 cm? (0) 2H,S() + 30:() —> 2802(g) + 2H:008) 10cm? (c) 2CsHio(g) + 1302(g) —+ 8CO,(g) + 10H, O(g) 260 cm? (d) 2H,S(g) + SO,(g) —> 3S(s) + 2H,0(®) 25cm? 1a2) 30 om? of nitrogen monoxide (NO) are mixed with 40 em? of oxygen to form nitrogen dioxide (N03). (@) Write a balanced equation to show the reaction. (b) What will be the final volume of the mixture? (Assume that all volumes are measured at the same temperature and pressure.) 3) If 30 em? of hydrogen and 18 em? of chlorine are left for a long time in a stoppered graduated tube in diffused light, write an equation ‘to show what will happen. Assuming all volumes to be measured under the same conditions of temperature and pressure, find volume of residual gas if the tube is opened (a) under mercury (b) under water. *4) 50 cm? of hydrogen and 15 em? of oxygen (both measured at s..p) are mixed together and heated to 160°C and then sparked. What will be the total volume after sparking if the volume is measured at (a) ssp. (b) 150°C and 770 mm Hg? 5) Ethane (C;H,) was burnt in a plentiful supply of ar. (@) Name the products of combustion. (©) Write an equation forthe reaction. (©) State the volume of oxygen which would react completely with 2dm? of ethane, (@ Assuming that air contains 20% oxygen by volume, find the volume of air that would be needed for the combustion. (All volumes are measured under the same temperature and pressure.) 6) A fuel gas contains (by volume) 50% hydrogen, 44% carbon monoxide, the other 6 being incombustible. (a) Write equations for the combustion of hydrogen and carbon monoxide, (®) Calculate the volume of oxygen required to bun 200 em? of ‘his fuel gas. (©) What volume of air would be required if air contains 20% oxygen by volume? (All volumes are measured at the same temperature and pressure.) * Optional question 122 7) To a mixture of 40 cm! of carbon monoxide and 60 cm* of methane (CHa), 200 cm? of oxygen were added and a spark was passed ‘Assuming constant pressure throughout in each case, calculate (a) ‘composition of the resulting gas (b) change in volume if all measure- ‘ments were made (i) at room temperature (i) at 120°C. 8) 40 cm? of a gaseous mixture of nitrogen and ammonia were passed repeatedly over heated copper(Il) oxide using syringes. When no further volume change occurred, the volume of residual gas was found to be 32 em, What was the composition by volume of the mixture? (Nitrogen does not react with heated copper(I) oxide but ammonia does 3CuO(s) + 2NHy(e) —> 3Culs) + Na(@) + 3H0(8) All gas volumes were measured at the same room temperature and pressure.) 9) 100 cm? of oxygen were partly ozonized and the volume became 940m? 302(g) == 203(g) Calculate the volume of ozone formed. (All volumes were measured at the same temperature and pressure.) 10) 10 em® of air were mixed with 10 cm? (an excess) of hydrogen and the mixture was exploded by sparking. After cooling, the volume was 14 om®, Caleulate the percentage by volume of oxygen in ai. (All volumes were ‘measured at room temperature and_pressure,) 11) A mixture of hydrogen and oxygen occupied 20 cm®. After explosion, 2 em? of oxygen remained (all volumes being measured at s.t-p.) What was the composition of the mixture? 12) 48 cm? of a mixture of methane (CH,) and ethane (CzHg) were exploded with 180 cm? of oxygen. After cooling to the original room temperature, the volume of residual gas was noted. It was found to decrease by 64 cm? when treated with potassium hydroxide solution ‘Assuming constant pressure throughout, calculate the composition by volume of the mixture. 13) 160 em® of a mixture of carbon monoxide, methane and hydrogen ‘were mixed with 250 cm? of oxygen and exploded. After cooling to the original room temperature, the volume of residual gas was noted. It was reduced by 110 cm? when shaken yyith potassium 123hydroxide solution, leaving 80 em? of excess oxygen. Assuming constant pressure throughout, calculate the composition by volume of the mixture. 14) When a mixture of carbon monoxide and carbon dioxide was exploded with excess oxygen, a contraction of 30 cm? was observed. ‘Another contraction of 65 cm? occurred on shaking the residual a5 with sodium hydroxide solution. Calculate the percentage composition by volume of the original mixture. (All volumes were ‘measured at the same temperature and pressure.) 15) 150 cm? of a sample of producer gas (a mixture of carbon monoxide, nitrogen and carbon dioxide) became 147 cm? when treated with potassium hydroxide solution. The resulting gas, when exploded with exactly the right amount of oxygen to burn it completely, gave @ mixture of guses. This mixture, when treated with potassium hydroxide solution, diminished by 465 cm®, 1005 cm? of undissolved gas remaining. From the above experimental results, and assuming that all volumes were measured under same conditions, deduce as far as possible the percentage composition by volume of the producer gas. 16) 60 cm? of @ gaseous mixture of methanol (CH; OH), propene (CH) and methane (CH,) were mixed with 325 cm? of oxygen and then ignited. The mixture, on cooling back to the original temperature (75°C), was found to have a contraction of 115 cm? in volume; a fuither contraction of 80 cm? occurred on treatment with potassium hydroxide solution. Assuming constant pressure throughout, find the composition by volume of the original mixture, 17) A gaseous mixture M contains hydrogen and hydrogen chloride only. When 100 cm? of M were exposed to sodium amalgam (Na/Hg) for 4 long time, the volume was reduced to 85 cm*. @) If 200 em? of Mf are added to 100 cm? of ammonia, what will bbe the volume of the final gaseous mixture? (b) What will be the effect on gaseous volume if the final mixture in (a) is shaken with excess dilute sulphuric acid? (Assume that all volumes are measured at room temperature and pressure.) (Hint: Hydrogen chloride would react with sodium (in sodium amalgam): 2Na + 2HCl—> 2NaCl + Hs) 124 MOLECULAR MASS AND GAS DENSITY 18) Find vapour density of each of the following volatile liquids: (@) Coie (©) (CGHs20 ©) CHCl, 19) What is the approximate vapour density of air, assuming that it consists of 79% nitrogen and 21% oxygen by volume? 20) An evacuated flask weighs 20.2 g. It weighs 20.44 g when filled with dry hydrogen, and weighs 28.72 g when filled with a dry gas G, temperature and pressure being kept constant. Find (a) vapour density (b) molar mass of gas G. #21) At 600°C and 810 mm Hg, the mass of 360 em? of phosphorus ‘vapour is 0.664 g. (2) Find volume of the phosphorus vapour ifit were at sp. (©) Determine the molecular mass of phosphorus (at 600°C and 810 mm He). #22) 1.20 g of an organic compound, vaporized at 127°C and 760 mm Hg, ‘occupy a volume of 328 cm®. Determine the molecular mass and vapour density of the compound. 23) A certain volume of a gas has a mass of 0.840 g while an equal volume of oxygen has a mass of 0.959 g, both measured at room ‘temperature and pressure. What is the vapour density and molecular ‘mass of the gas? Is the gas lighter or heavier than air? MOLECULAR FORMULAE OF GASES AND VOLATILE SUBSTANCES 24) From the fact that the vapour density of phosphorus is 62, deduce the number of atoms in a phosphorus molecule 25) At the same room temperature and pressure, 6.4 g of oxygen occupy the same volume as 8.0 g of argon. Use this information to calculate the relative molecular mass of argon and the number of atoms present in 1 molecule of argon. 26) Two volumes of a gaseous hydride of an element £ yield three volumes ‘of hydrogen on thermal decomposition. What is its simplest formula if all volumes were measured at the same temperature and pressure? * optional question. 12s27) X is a gaseous compound of silicon and hydrogen; its density at room temperature and pressure was found to be 1.333 g dm. 50 cm* of X upon complete decomposition gave 100 cm? of hydrogen, (All volumes were measured at the same temperature and pressure.) (a) What is the molecular mass of X? (b) Deduce the number of hydrogen atoms in one molecule of X. (©) What is the molecular formula of X? 28) 30 em? of hydrogen fluoride gas, HF(g), combine with 15 em? of 1 gus X to form 30 om? of a gas ¥ and no other product. Gas X has an empirical formula NF(g) and its vapour density is 33. (All volumes ‘are measuced at the same temperature and pressure.) (a) What is the molecular mass of gas X? (b) What i the molecular formula of gas X? (©) What is the molecular formula of gas ¥? 29) The formula of a gaseous oxide of nitrogen Nyy can be determined by the following experiment. Ww before experiment after experiment At room temperature and pressure 100 cm? of the gas NxOy were Put into the hard glass tube. The spiral of iron wire was then electrically heated to red hot. The gas NxO, was completely decomposed into its elements; and oxygen so produced was combined with iron wie. After 20 minutes, the volume of nitrogen was found to be 50 cm? at room temperature and pressure. (@) How many volumes of nitrogen was decomposed from 2 volumes of Ny0,? 126 (b) How many molecules of nitrogen are contained in 2 molecules of NxOy? (©) How many nitrogen atoms are contained in 2 molecules of Nx0y? (@ What isthe value of xin N,O,? (@) The vapour density of NyOy was found to be 15. What is the relative molecular mass of NyOy? (®) Cateulate the formula of N,Oy. (C.DC. sample question) 30) A non-metal chloride has a vapour density of 51.5, and contains 68.9% by mass of chlorine. (a) What is the molecular mass of the chloride? (b) How many atoms of chlorine are there in one molecule of the chloride? 31) 20 cm? of a hydrocarbon of empirical formula C3Hs gave 80 cm’ of carbon dioxide when it was but completely. (All volumes were measured at s.p.) Find its molecular formula. 32) $0 cm of a hydrocarbon of formula CxHy required 150 cm? of ‘oxygen for complete combustion, both volumes being measured at the same temperature and pressure. Calculate the value of x. 33) 160 cm? of oxygen were added to 40 cm* of a gaseous hydrocarbon, After explosion and cooling to room temperature, the residual gas ‘occupied 140 cm®, After treatment with potassium hydroxide solution, 60 cm? of oxygen remained. Find the molecular formula Of the hydrocarbon, assuming all volumes were measured at the same temperature and pressure 34) When 15 am? of a gaseous hydrocarbon H were mixed with 70 em? of oxygen (an excess) and ignited inside a graduated tube in the presence of concentrated sulphuric acid, the volume of the residual gas was 475 cm?, This was reduced to 17.5 cm® by treatment with caustic potash. All volumes were measured under the same conditions of temperature and pressure, Find the molecular formula of the hydrocarbon H. (HKCEE) 22735) A mixture of propane (C3Hs) and an alkene occupied 48 cm’. To bum the mixture completely, 228 cm? of oxygen were required, and after combustion, 144 cm? of carbon dioxide were left. (All volumes were measured under room conditions.) Calculate (2) the molecular formula of the alkene (b) the composition of the mixture by volume. (Hint; Let the molecular formula of alkene be CxHax.) 36) 166 cm? of an organic compound containing only carbon, hydrogen and oxygen required 996 cm? of oxygen for complete combustion. ‘The volumes of carbon dioxide and steam formed were found to bbe 664 cm? and 830 cm® respectively. Find the molecular formula of the compound, if all volumes were measured at 120°C and 750 mm Hg pressure 37) 24 cm? of a monohydric alcohol vapour were mixed with $1 cm? ‘of oxygen and exploded. After cooling, the volume was reduced by 36 cm?. Treatment with sodium hydroxide solution caused a further contraction of 24 cm?, Find the molecular formula of the alcohol, assuming all volumes were measured under room conditions (int: Let molecular formula of the monohydric alcohol be CyH,0.) 38) On combustion, 300 cm* of a gaseous hydrocarbon form 900 em? of carbon dioxide and 0.7232 g of water. Assuming all volumes to ‘be measured at s.t.p., find the molecular formula of the hydrocarbon. 128 9 METAL REACTIVITY SERIES METAL REACTIVITY SERIES Metal reactivity series is a list of metals arranged in descending order of reactivity. Metals at the top of the series are most reactive and those at the bottom: are least reactive. The arrangement is usually based on the vigour with which metals react with air (or oxygen), water and acid. ‘A metal activity series for some common metals is shown below: pousium —K most reactive sodlum Na acum mapwium Mg | aluminium Al secty zine zn decent ron Fe lead Pb compe: cu mercuy He siver Me gold au least ative 129Pb : extremely dilute HCI react with decreasing vigour (K : explosively; Mg : vigorously; Fe no action steadil slowly) to form salt and Hh > MgCl (aq)+H (2) fn case of Mg, Al, Zn,Fe)|e.g. Mg(s) + 2HCI(aq) leg. Ca(s) + 2H; 008) | no action, steam slowly) to form > Ca(OH), (6) +H(8)) Zn(s) + H; (2) = Zn043)+H(3) Reaction with react with decreasing ligour (K : explosively; lt, and metal hydroxide ln case of K, Na, Ca) Fe Teact with decreasing vigour (K : violent ‘cold water (6) Mg : very slowly) to > 2NaOH(aq)+H;(@)or H, and metal oxide no action form metal hydroxide and Hy leg. 2Na(s) + 2H; 0(@) | = 2Na, (6) a ; Heating in air or oxygen S $ Zz eg. 4Nals) + Os do not burn, but only form a ge is bum fiercely to form oxide surface layer of oxide no action 5 ft remain shiny even after prolonged exposure to atmosphere Appearance of metal dull, stored under oil generally dull after usually exposure to atmosphere REACTIVITY OF METALS TOWARDS AIR, WATER AND ACID K Na Mg Al Zn Fe Pb cu He Ag Au Metal In many cases, the above table can be used to make sensible predic- tions about reactivities of metals. Study the following example. Example 9.1 What would you expect to see when (a) a copper foil is heated strongly in air? b) a small piece of rubidium (Ru) is added to cold water? (Ru is above K in the metal reactivity series) (e) steam is passed over strongly heated bismuth (Bi)? (Bis below Pb in the series) (d) a small piece of tin (Sn) is added to ditute hydrochloric acid? (Sn is Between Fe and Pb in the series) Give equations where appropriate. (@) The reddish-brown copper would form a black coating of copper(I) oxide 2Cu(s) + On(g) —> 2Cu06) () Rubidium would react very violently with cold water, a flame being observed. 2Rb(s) + 2H, 0(8) —> 2RbOH(aq) + Ha(g) (©) No visible change (as there is no reaction). (@ Tin would react with hydrochloric acid slowly, colourless gas bubbles (H,) being evolved, Sn(s) + 2HCI(aq) — SnCl,(aq) + Ha(@) In general, reactivity of a metal may be predicted based on its position in the reactivity series, but there are exceptions. For example, zine reacts with steam at a moderate rate; since aluminium is higher than zinc in the reactivity series, it might be expected that aluminium would react with steam even more vigorously, However, aluminium has no apparent reaction with steam at all. This is because aluminium metal is usually covered with a thin, firm layer of aluminium oxide which protects the metal from reacting with steam. DISPLACEMENT REACTIONS OF METALS IN AQUEOUS SOLUTIONS ‘A metal will displace any metal lower in the reactivity series from solution of its sat (but not vice versa) 131Take the example of copper and silver. Copper is higher than silver in the reactivity series, so copper would displace silver metal out from : silver nitrate solution (ie. copper ‘dissolves’ and silver metal comes out): Cus) + 2AB"(aq) —> Cu*(aq) + 2Ag66) On the other hand, if a piece of silver is dropped into copper(I) sulphate solution, no reaction will occur. a no sction metal oxide or metal ‘sulphates sulphate does not exist decompose with increas ea BFeSOcG) ‘slphur tnoxide Example 9.2 What would you expect to see when (a) an iron sheet is placed in copper(II) sulphate solution f] (6) @ piece of platinum (Pt) is placed in iron(II) sulphate solution { (Ptis below Ag in the reactivity series) i Give ionic equations where appropriate. i hydroxides SCu6¢8) 71,008} hydroxides do not exist (@) The iron sheet would be coated with a reddish brown layer of copper and would become thinner. The blue colour of copper(II) solution would gradually fade Fe(s) + Cu?*(aq) —> Fe™(aq) + Cu(s) mn FCuWNO, (6) nitrates +6@) +0: n dionide and oxy ge SENS +0.) > 2CH003)*4NOsG) > TAgG)*2N0, (@) open dix en s decompose with increusing |decompose with ‘decompose to nitrite nd oxygen 22. 2KNO, eae to metal oxide, ‘decompose to metal SAgNOs nitrate does not exist, (b) No visible change (since platinum is below iron in the reactivity series), ee Action of heat on Example 93 W, X, ¥ and Z are metals, W displaces X from a solution of nitrate of X and displaces ¥ from a solution of sulphate of Y, but has no reaction with a solution of chloride of Z. ¥ displaces X from a solution of nitrate of X. Arrange W, X, Y and Z in decreasing order of reactivity. +0.) 0, FO carbonate does not exist | 20118) SG8)+ cox) ng: E Ing eae to metal oxide and carbon dioxide loxyese and carbon dioxide ‘carbonates decompose with increas- ee [decompose to metal, ee Since W can displace X and Y but not Z from aqueous solutions of their salts, it can be deduced that W is more reactive than X and Y, but less reactive than Z; so the order would be ZWXY or ZWYX. By similar reasoning, Y should be more reactive than X. The order is thus ZWYX. SEE # EAS ow oxides no action THERMAL STABILITY OF COMPOUNDS OF METALS Generally reactive metal forms stable compounds. Thus the higher the position of a metal in the reactivity series, the more stable towards heat would be its compounds. Study the following table. se decompose to metal Snd oxygen Na ca Me. Al Zn Fe Pb ou Hg Ag Au 132 133REDUCTION OF METAL OXIDES Reduction may be simply defined as the removal of oxygen from ‘a substance. (A full account of reduction and oxidation will be given in Chapter 10.) In general, the ease with which a metal oxide can be reduced depends fon the position of the metal in the reactivity series. The lower a metal in the series, the easier could its oxide be reduced by carbon, carbon monoxide or hydrogen. Reduction of oxides by heating with C or CO th (1000 1500°c) | (2000 1s00°e) | _sother metal K any metal can reduce oxide of Ne another metal eae below it in the series Mg zo action eg. Mg(s) + PbO) = Mz0(s) a + Pos) Zn | reduced with Fe cna C0) Teduced with eg, PbO() + Increasing ease > POCO; (4) ¢8-POO(S)*HL@) Ld Cow) OF Pas) O® co Hg ag decomposed to metal by heat alone Au Example 9.4 What would you see when each of the following is heated with Bunsen burner? (a) Mercury(It) oxide (6) Lead{It) nitrate crystals (e) A mixture of copper II) oxide and carbon 134 (d) A mixture of magnesium oxide and silver Give equations where appropriate (@) The red powder (HigO) would change to a silvery liquid(Hg), and a gas which rlights plowing splint would be evolved. 2Hg0(6) — 2H1g(®) + 0308) (©) Brown fumes (NO») would be evolved and a solid residue (P60) which is orange when hot but yellow when cold would be formed. 2Pb(NO;)2(3) —> 2PbO(s) + 4NO2(g) + O2(g) (©) The black powder (CuO) would change to reddish brown powder(Cv). CuO{s) + C6) —+ Cuts) + COV); CuO{s) + CO() — Cuts) + C03) (2) There would be no visible change. Example 9.5 ‘Some reactions of the compounds of four metals P, Q, R and $ are investigated and the results are as follows: (4) On heating, the carbonates of Q, R and S are decomposed but that of Pis not (ii) On heating, the nitrates of P, Q, R and S are all decomposed, but ‘that of Q decomposes to leave the metal. (iti) On heating with carbon using Bunsen flame, oxides of Q and R change into the metals while those of P and S are not. From the above information, arrange the metals P, Q, R and S in decreasing onder of reactivity. Give your reasoning briefly. From (i, P is the only metal whose carbonate does not decompose ‘on heating. So P must be the most reactive metal, From (ii), only the nitrate of Q decomposes to give the metal on heating. So Q must be the least reactive metal among the four. From (li), it can be deduced that Sis more reactive than R. ‘Thus the order would be PSRQ. EXTRACTION OF METALS With the exception of very unreactive ones (eg. gold), metals are Found in Nature as compounds rather than free elements 135‘The obtaining of a metal from its ore is called extraction. ‘There is a close relationship between the position of a metal in the reactivity series and the year when the metal was first extracted (discovered) by Man in a reasonably pure state — the lower the position of a metal in the series, the more ancient would be the year of discovery. For example, sodium was first extracted in A.D. 1807, zinc in A.D. 1000, and gold around 5000 BC. (about 7000 years from today). Such relationship exists because a less reactive metal would form less stable compounds, and could therefore be obtained in pure state more easily ‘As time went by, more effective methods of extraction (eg. by clectrolysis) were invented, so even reactive metals could be obtained from their stable compounds, In general, metals at the top of the reactivity series (K to Al) are usually extracted by electrolysis of their molten compounds; metals in the middle of the series (Zn to Pb) are often extracted by reduction of their oxides with carbon; metals at the bottom are often extracted by heating the ores alone or by displacement from aqueous solution of their salts. Example 9.6 The following table gives information about four metals M, N, Q and R. Metal ‘Reaction of metal orits compound | Year of discovery room +H20 Iydroxide of M— | A.D. 1808 M | M+H; Tams otros le of (moderate rate) Theat NW | nitrate of “+ Ny (a tiquid metat at | BC. rtp.) (year not +brown fumes recorded) Q | QF aqueous solution of ntrate of N BC room _, v4 aqueous solution of (year not conditions” "* nitrate of @ recorded) Q+ dilute HCI —> no reaction heat 10 1500°C R_ | oxide of R+CO——" + R+00;| A.D. 1000 heat t0 1500°C | no oxide of Rt Hy rasctien (a) Suggest what M,N, Q and R might be, Give your reasoning. (6) Arrange the metals M, N, Q and R in decreasing order of reactivity. (c) What relationship exists between the order of reactivity in (b) and the years of discovery of the metals? (@) M might be calcium. Calcium would react with cold water to give calcium hydroxide and hydrogen at a moderate rate. WV is mercury. Mercury(II) nitrate and silver nitrate would decompose on heating to give metal, nitrogen dioxide (brown fumes) and oxygen. Since WV is a liquid metal, it should be mercury. Q might be copper. Since Q has no reaction with dilute hydrochloric acid, it should be below lead in the reactivity series (ic. it may be copper, mercury, silver or gold). But Q displaces V (mercury) from an aqueous solution of nitrate of N, therefore Q is more reactive than mercury. It is therefore likely to be copper. R might be zinc. Zine oxide could be reduced to metal by carbon ‘monoxide but not by hydrogen at 1500°C. (b) MRON (©) The lower the position of a metal in the reactivity series, the more ancient would be the year of discovery. EXERCISE 9 1) Several experiments are carried out to determine the reactivities of metals A, B, C, Dand £. The results are tabulated as follows: Metal A B c pie Action of water | no 20 reacts | no reacts ‘on metal reaction | reaction | vigorously} reaction | slowly Action of dilute reacts to | reacts to] reacts to hydrochloric | no no liberate | liberate | liberate acid on metal | reaction | reaction | Hz Hy | Ha Heating the oxide | oxide oxide of metal | reduced | reduced | "| BO ne witheatton |toAn (tgp | ‘action | reaction | reaction Displacement | B displaces A from reaction ‘an aqueous solution] — — | of the nitrate of A 136 137a» 3) 138 (@) Arrange the metals A, B,C, D and E in decreasing order of reactivity, (&) Which metal will tamish most rapidly in ait? How is it stored in laboratory? (© Only one of the metals gives rise to a strong alkali. Which one? (@ When the nitrates of these metals are heated, only one decomposes to leave the metal. Which is the most probable one? (€). Which metal is most likely to be found free in Nature? (0) How is metal C extracted from its ore? ‘A metal Mf reacts vigorously with cold dilute hydrochloric acid but has virtually no reaction with cold water. If it is heated in steam, it glows with an intense white light, a white solid V being formed and a colourless gas G liberated. (@) Suggest what M,N and G might be. (b) How would you test gas G to see if your conclusion is correct? (©) Write balanced equations for thermal decomposition of the nitrate and carbonate of Mf. (@) Metal M forms M?* ions. Write an ionic equation to represent the reaction that occurs when a piece of M is added to aqueous copper(I!) sulphate. ‘The following table gives information about three metals P, Q and R. P @ Rg ‘Method of | under | no precautions | in airtight box storage oil needed ection of | 00 changes froma | no change in colour heat on | change | green powder to.a | but catbon dioxide carbonate back powder; | given off carbon dioxide siven off (@) Arrange the three metals in decreasing order of reactivity. (b) Suggest what P, Q-and R might be. (©) For cach of the following, describe briefly what you might 8 observe. (@ Pis added to cold water. (i) Hydrogen is passed over heated oxide of Q. (ii) R is mixed with the oxide of Q. The mixture is heated strongly. 4) Explain each of the following: (@) Aluminium does not react with steam in spite of its relatively high position in the reactivity series. (b) Copper{I) sulphate solution cannot be kept in an iron bucket. (©) Iron is not obtained industrially by heating iron(III) oxide with ‘magnesium, though this isan effective method. (@) Gold isoften made into omaments. (@) Zinc can be extracted from its compounds by electrolysis. Yet in practice, itis extracted by heating its oxide with coke. 13910 REDOX REDOX REACTIONS ‘The word redox is a shortened form for reduction-oxidation. A reaction which involves oxidation and reduction is often termed redox reaction. In fact oxidation and reduction must occur simultaneously — no oxidation can take place without reduction, nor reduction without oxidation. Redox in terms of oxygen or hydrogen Early definitions of oxidation, reduction, oxidizing agent and reducing agent are: Oxidation: Addition of oxygen to (or removal of hydrogen from) a substance. Reduction: Removal of oxygen from (or addition of hydrogen to) a substance. Oxidizing agent: A substance that brings about oxidation by giving oxygen to (or removing hydrogen from) another substance. Reducing agent: A. substance that brings about reduction by removing ‘oxygen from (or giving hydrogen to) another substance. ‘Thus in a redox reaction, a substance being oxidized serves as reducing agent; a substance being reduced serves as oxidizing agent. For example, reduction (removal of oxygen) ercapeereamene) PbOG) + CO()—> PHS) + COr(e) oxidizing reducing agent agent oxidation (addition of oxygen) 140 Example 10.1 Consider the redox reaction: Mls) + HyO(g) —> MgOts) + Ha(s) State, with reasons, the reactant which is (a) oxidized (6) reduced (c) the oxidizing agent (d) the reducing agent (2) Mg. Mg is oxidized because oxygen is added to it to form MgO. (b) HzO. H,0 is reduced because oxygen is removed from it to form H. (©) HzO is the oxidizing agent because it gives oxygen to Mg, (@) Mgis the reducing agent because it removes oxygen from HO. Redox in terms of electron transfer Modern chemists usually define oxidation and reduction in terms of electron transfer. OXIDATION is regarded as loss of electrons, and REDUCTION as sin of electrons. (Remember the word ORE ~ Oxidation isthe Removal of Electrons) ~ ~ ‘An OXIDIZING AGENT is an acceptor of electrons, and a REDUCING AGENT is a donor of electrons. For example, oxidation (loss of e°) 2Mg6)_ + Os(@) ——> 2Mg"0"G@) reducing oxidizing agent agent reduction (ain of €) A substance cannot lose electrons unless another is present which can gain them, thus it is evident that oxidation and reduction must take place together. Example 10.2 Consider the redox reaction: Znjs) + Cu*(aqg) —+ Zn**(aq) + Cu(s) State, with reasons, the reactant which is (a) oxidized (b) reduced (c) the oxidizing agent (d) the reducing agent. 141(a) Zn.Zn is oxidized because cach Zn atom loses 2 electrons to form Zn** ion. (b) Cu**.Cu?* is reduced because each Cu?” ion gains 2 electrons to form Cu atom. (©) Cu?*.cut* is the oxidizing agent because it accepts electrons from Zn. (@ Zn.2n is the reducing agent because it donates electrons to Cu**. Half-equation Equation for a redox reaction can be split into two halves — one hhalf-equation shows oxidation, while the other shows reduction. The change represented by a half-equation is called half-reaction. A single half-reaction can never take place alone. Example 103 For the equation mentioned in Example 10,2, write two half-equations involving ions and electrons — one for reduction and one for oxidation. cu"(ag) + 28 —> Cu(s) (reduction) Zn(s) —> Zn*"(aq) + 2€ (oxidation) OXIDATION NUMBER Many redox reactions (eg. the reaction in Example 10.3) are easy to explain in terms of electron transfer. However, some reactions are clearly redox (eg. C(6) + O2(g) —* CO3(g) ), but itis not easy to see hhow electrons are transferred. To deal with such cases, the concept of oxidation numbers useful. Oxidation number is a charge (imaginary in many cases) assigned to.an element ina substance. The oxidation number (O.N.) of an clement in an ionic compound is defined a8 the number of electrons which have to be removed from (ON. = #ve) or guined by (O.N. = —¥e) an atom of the element in order to convert it from the free (uncombined) state into that in the compound. We take magnesium oxide, MgO, as an example. In order to convert a Mg atom into a Mg?” ion in MgO, two electrons have to be removed from the Mg atom, therefore the oxidation number of Mg in MgO is + 2. 142 Altematively, we can say magnesium in MgO is in the oxidation state of + Il and represent it by Mg({I). On the other hand, two electrons have to be added to an oxygen atom to form an 0? jon in MgO. Thus the oxidation number of O in MgO is ~2, and its oxidation state is —II, represented by O(-II). Note that the sign of an oxidation number always comes before the number. Arabic numbers are used to designate oxidation numbers, while Roman numerals are used to designate oxidation states. Note also that the “+” sign before a Roman numeral is often dropped out thus we usually write Mg(II) instead of Mg(+HI). Oxidation number can also be assigned to elements in covalent compounds by making use of the electronegativity concept. (Electronegativity may be roughly defined as the ability to attract, electrons. Thus an element with greater attraction for electrons has a higher electronegativity value.) Oxidation numbers are assigned by taking them to be equal to the charges which various atoms in a compound would carry if all bonds in the compound were imagined to be ionic instead of covalent. In doing so, a shared pair of electrons between two atoms is assigned to the atom with greater electronegativity. On the other hand, if two atoms are alike, the shared pair is split between the two, one electron being assigned to each atom. The resulting charges on various atoms when bonding electrons are assigned in such a way will be the ‘oxidation numbers of atoms in the compound. In the Periodic Table, electronegativity increases as shown below Increasing clectronegativity cs Rules for assigning oxidation numbers To assign oxidation numbers, the following rules should be observed: (1) All elements in free (uncombined) state have oxidation numbers of zero, eg. the oxidation number of nitrogen in nitrogen molecule Nz is zero, and that of copper in the free element is also zero. (2) The oxidation number of an element existing as simple ion is both numerically and algebraically equal to the charge on the ion, 143eg. MgO contains Mg?* and 0" ions, the O.N. for Mg in this ‘compound is +2, while that for O is -2. (3) The oxidation number of all Group I metals (alkali metals), ‘eg. Na,is always +1 in their compounds. (4) The oxidation number of all Group I metals (alkaline earth metals), eg. Ca, is always #2 in their compounds. (5) The oxidation number of hydrogen is often +1 in its compounds (except in metallic hydrides, eg. NaH, where itis ~1).. (©) As fluorine is the most electronegative element, it has oxidation ‘number of —1 in any of its compounds. (7) Oxygen, second only to fluorine in electronegativity, has an oxidation umber of —2 in almost all ts compounds. °F Mp0 Fed, CO, (Exceptions: in peroxides, oxygen has an O.N. of —1 in F,0, oxygen has an O.N. of +2) (8) The algebraic sum of oxidation numbers of all atoms in a compound (uncharged) is zero. In a polyatomic ion, the algebraic sum is equal to the charge on the ion. “8 6 Md GOH 86> For Hz0, (H) X 2 + (-2)= 0 Nacl, (1) + C1) 0 CH, (-4) + (H)X4 = 0 OH, (-2)+ GI) -1 80", (46) + (2X4 = 2 (@) In compounds containing more than two elements, the oxidation umber of any one of them may have to be obtained by first assigning reasonable oxidation numbers to the other elements. Eg. in KMnO,, reasonable oxidation numbers which can be assigned are #1 and —2 for potassium and oxygen respectively; since (+1) + (ON. of Mn) + (2 = 0, ON. of Mn inKMn0, = +7 (10)The oxidation number of an element may vary from compound to ‘compound. Even in the same compound, different atoms of an element ‘may have different oxidation numbers. °S RuNos , GiGi on 144 Example 104 Find oxidation numbers of underlined elements in the following ‘compounds or ions: (a) [CufNH)3]?* (b) Ks{Fe(CN}o) (c) NazCr0, (d) (i) NHsNOy (it) NH.NOs (e) (i) CHyCH,OH (ii) CHyCH,OH (f) (i) CHyCHO (ii) CH,CHO Let y be the oxidation number of the underlined element in each (@) Since NH is electrically neutral, the algebraic sum of the oxidation numbers of atoms in it is zero, ytOX4= 43; = y=e Oxidation number of Cu in [Cu(NH3)s]?" = +2 (©) CN” group has 1 negative charge GY X3+y+ Cx 6=0 = y=# Oxidation number of Fe in Ky [Fe(CN).] = +3 © GX 242 #C2)K7=0 = y= +6 Oxidation number of Cr in NazCr20, = +6 (2) NH.NO, isan ionic compound consisting of NH,’ and NOs ions (® For NH’, y #1) X 4 * y=3 Oxidation number of N in NH.’ = —3 (i) For NOs, yt(Qx3e- - ya4s Oxidation number of N in NOs = +5 © HH \ H-¢-C-0-H ethanol HH ‘There is no difference in electronegativity between the two carbon 145© 146 ‘atoms joined by the C—C bond. It follows that 4 I Algebraic sum of oxidation numbers of atoms in H-C- is O; ! & algebraic sum of oxidation numbers of atoms in so @ ytOx3=0 ye (CHsCH, 0H) (i) y+ 1) x3 + (-2)=0 yl (CH, CH, 0H) 4 \ H-C-C=0 —_—thanal ea HH Similar to (), a pera sm of oxidation number oF atoms in =, algebraic sum of oxidation numbers of atoms in is. (@ Oxidation number of C= -3 (CH, CHO) Gi) Oxidation number of C= +1 (HCHO) Note: When ethanol (CHs CH, OH)is oxidized to ethanal (CH, CHO), the carbon atom in the methyl group (CHs—-) undergoes ‘no change in oxidation number, while the oxidation number a of carbon atom increases from —1 in —C-O-H_ to +1 t H jn -C=0. Therefore in oxidation of ethanol to ethanal, # only the ~CH,OH group is oxidized to form —CHO group, the CH group being unaffected. Defining redox in terms of oxidation number Now we are in a position to give an alternative definition of redox in terms of oxidation number. ‘A redox reaction may be viewed as a reaction in which reacting substances undergo changes in oxidation number. In oxidation, oxidation ‘number increases; in reduction, oxidation number decreases. Let us illustrate the above definitions by the redox reaction mentioned in Example 10.2. reduction (decrease of ON. from 42 to 0) Cu(aq) + Za(s) ———> 2n"(aq) + Cuts) oxidizing agent reducing agent | Le station (increase of O.N. from 0 to #2) Note: The above equation can be viewed as 2 combination of two hhalfequations, These can be written as Cu*(aq) + 26° —> Cus) (reduction) Zn(s) —> Zn**(aq) + 2 (oxidation) or Cu(ll) + 2° —> Cuo) (eduction) ZO) —> Z(t) + 20° (oxidation) but not as Cu(#+2) + 20 —> Cu Zn —> Zn(42) + 26 Example 10.5 State which of the following are redox reactions and which are not. Explain briefly. (a) HCVaq) + NaoH{aq) ——> NaCi(aq) + #0(%) (b) Ag'(aq) + C'taq) = —— Ags) (c) 2KC10s(s) —— 2K As) + 30/8) (d) SiO,(s) + CaO{s) _— ——+ CaSiOs(s) fe) 2AgNO3(aq) + Cufs) ——+> Cu{NOs (aq) + 2A8(s) (f) Cllalg) + 20s(¢) = ——> COn{g) + 2H2012) (@), (©), (@) are not redox reactions because the reacting particles undergo no change in oxidation number. 147(©, ©, (P) ate redox reactions. In (©), oxidation number of chlorine changes from 45 to —1 oxidation number of oxygen changes from —2 to 0. a ©), oxidation number of silver changes from #1 to 0 oxidation number of copper changes from 0 to #2. ‘In (P), oxidation number of carbon changes from —4 to +4 oxidation number of oxygen changes from 0 to ~2. COMMON OXIDIZING AGENTS Reagent Eiectve change (Change in oxidation state Oxygen 038) + 20°46) 2081 @q) | 0(0) > OT Chlorine Ch) > 2CT aq) oF (9) 1) + cx- Bromine Br, @) “> 2B faq) oF (6) Br(0) > Be) Dilute HNO, NO,"taa) > NOG) Nev) > Nab Concentrated HNO, NOs“(eq) > NO, @) Nw) > Nav) Concentrated H:S0, | $0,°°(@) > $0s(@) sev > savy Manganese QV) oxide | MnO (s) > Ma**(aqy KMn0, i acide solution | MnO, aq) -> Ma**(eq) KMn0, in alkaline solution] MnO, aq) > MnO, (6) K,CrxO, inacidic solution | Ct,0,*"(@q) ~* 2Cr°* faq) MndV) * Maan) Macvit) > Madly Mncvmt) -> Minav) Gv > cat COMMON REDUCING AGENTS Reagent ‘Bective change (Change in oxidation state Metals high in the | atom -> positive fon reactivity series. | e.g, Nas) > Na“) oF Na" (aq) Na@) > Nay (es. Na) Hydrogen H.@ > 2H"Gq) HO) > Ha carbon Ws) + COE) oF COs.) C(O) * Caer ayy Carbon monoxide | CO@) + COs.) ca) > cav) Ammonia 2NHa@) > Na) NEM > No) ms. Sq) > Si) StI) > s(0) Sulphiter 80,""(ea) ~ SO2aq sav) > svn Trond) sats | Fe?aq) > Fe'%aa) Fe(ll) + Peat lodides 21a) + bea) 1) > 10) 148. Example 10.6 Classify the reagents Kis), Ag'(aq), Fo(g) Cag), Fe(s), Fe**(aq), Fe*“(aq), $03(g) under the headings: (a) Those which can act only as an oxidizing agent (b) Those which can act only as a reducing agent (c] Those which can act either as an oxidizing agent or a reducing agent, Justify your answers in cases of K(s), Ag*(aq) and SO2/¢). @) Ag‘G@q), Fa), Fe*(aq). ‘Ag'(aq) can act only as an oxidizing agent and never as a reducing agent because the oxidation number of silver in Ag‘(aq) can never be increased ~ it is +1 in Ag’ and can be changed to 0 but not to any number greater than +1 (6) K(s), CV(aq), Fels) K() can act only as a reducing agent and never as an oxidizing agent because the oxidation number of potassium in K(6) can never bbe decreased — it is O in K and can be changed to +1 but not to any negative values (©) Fe*aq), $0.) $O,(g) can act either as an oxidizing agent or a reducing agent because the oxidation number of sulphur in SO3(g) is +4 when it changes to U(in S), SU2 acts as an oxidizing agent; when it changes to +6 (in $0.*), SO acts as a reducing agent. BALANCING REDOX EQUATIONS In balancing a redox reaction, the reactants and products must, of course, be known, There are two common methods to balance a redox reaction: 1. Using halfequations (involving ions and electrons) 2. Using half-equations (involving oxidation states) Study the following examples. Example 10.7 Use the half-equation method (involving ions and electrons) to balance HNOs + HS —> NO+S +130 49The principle is to find two half-equations, one for the oxidizing agent, another for the reducing agent, and then combine them together to give the final balanced equation. ‘Step 1 Find the oxidizing agent and see what it is reduced to, Oxidizing agent: NO}, reduced to NO NOs —+ NO oe 0 Step 2 Balance the number of atoms in () by (a) multiplying by a suitable factor on one side (b) placing suitable number of HzO, H’ or OH on any side. In ()), there is 1 nitrogen atom on either side, thus (a) is not necessary here. ‘There are 3 oxygen atoms on LHS. and only 1 oxygen atom on RH. To balance the number of oxygen atoms, we apply (b) and add 2H;0 to RAS. NOs —+ NO + 24,0 eoodd - w To balance the number of hydrogen atoms, we add 4H" to LHS. NO; + 4H” —+ NO + 2H,0 oo il) Step 3 Balance the number of charges by adding suitable number of electrons on LHS. Total charge on LHS. = (I) +4 = 34 Total charge on RHS. = 0+2X0 = 0 So we add 3e” to LAS, NOs + 4H" + 3e° —> NO + 2H,0 w) Step 4 Find the reducing agent and see what it is oxidized to. Reducing agent: S, oxidized to S FF 305 pocoonsonsepoboseeepucesonnnce (C) Step 5 Balance the number of atoms in (v) by (2) multiplying by a suitable factor on one side () placing suitable number of HO, Hor OI on any side, (@) and (b) are not necessary in this case ‘Step 6 Balance the number of charges by adding suitable number of electrons to RHS. 150 We add 2e" to RHS. Sorcerer eee eee es Wi) (iv) and (vi) are the two required halfequations involving ions and electrons. ‘Step 7 Combine the two halfequations by eliminating the electrons. (iv) X 2 2NOs + 8H’ + 6e” —> 2NO + 44,0 (wii) (i) X 3 38> + 38 + 6 : (iil) (vi) + (Vil) 2NO; + 8H" + 38" — 2NO+38+4H,0 ... Gx) ‘Step 8 If an ‘ordinary’ equation is required instead of the ionic one, (ix) can be rewritten as 2HNOs + 3H:S —> 2NO + 38 + 41,0 & Example 10.8 Use the half-equation method (involving oxidation states) to balance HINOs + H,S — NO +S + 1,0 ‘Step 1 Find the element in the oxidizing agent whose oxidation number is decreased in the reaction, Indicate the change. Oxidizing agent: HNO} Element whose oxidation number is decreased: N Nv) — Nall) : “0 Step 2 Balance the charge in (1) by adding suitable number of electrons to LHS N(V) + 3 —> N(ll) (i) Step 3 Find the element in the reducing agent whose oxidation number is increased in the reaction. Indicate the change Reducing agent: Wa Element whose oxidation number is increased: $ S(t) —> s(0) ai) ‘Step 4 Balance the charge in (ii) by adding suitable number of electrons to RAS. 1stSCID) —> S(0) + 26 ce eeeee (ii) and (jv) ate the two half-equations involving oxidation states. ‘Step 5 Combine the two half-equations by eliminating the electrons. Gi) X 2 2N(V) + 6" —+ 2NAIT) moonposnnnn (0) (w)X 3. 35(-I1) — 38(0) + 6 e (wi) () + (i) 2N(V) + 38-11) — 2NAID + 38(0) . (vi) ‘Step 6 Replace each term by its original ionic or molecular formula. 2HNO, + 3H,S — 2NO + 3S (not balanced) (itty ‘Step 7 Balance the equation by adding suitable number of H;0, H’ or OW to any side In this case, we have to add 4H,0 to RHS. 2HNO, + 3H,$ —> 2NO + 35 + 41,0 Example 10.9 Chlorine water is added to potassium iodide solution, (a) What is the colour of (i) ehlorine water (ii) potassium iodide solution? () What colour change takes place when the two solutions are mixed together? Explain the colour change, (ec) Write the oxidation half-equation for the reaction. (d) Write the reduction half-equation for the reaction, (e) Give the ionic equation for the reaction that occurs (@) (Very pale greenish yellow (ii) Colourless (b) A brown coloration appears immediately, Chlorine Cl, oxidizes iodide ions 1”(aq) to liberate 13(aq) which is brown in colour. (©) 20 (aq) + (aq) + 22 (@) Chz(aq) + 2¢° — 2€¥ (ag) (©) Cha(aq) + 21"(aq) — 2C1'(aq) + (29) Example 10.10 (a) Write an ionic equation for the reaction between acidified potassium permanganate and iron(i1) sulphate solution. 152 (b) State the number of moles of FeSO, which would react with 1 mole of KMn0s. (a) Referring to the table of common oxidizing agents, we see that in acidic medium, MnO, is reduced as follows: MnO, —> Mn™* Using the method discussed in Example 10.7, we would get MnO, + 8H" + Se —> Mn? + 4H,0. » SEe** > SFei+ Se MnO, + SF" + 8H'—> Mn™ + SFe* + 4H,0 (b) From the equation, 5 moles of FeSO, would react with 1 mole of KMD, EXERCISE 10 1) Find the oxidation number of each of the underlined elements in the follewing compounds or ions: (@) HNO; (©) Naz$05 (©) Ke [Ee(CN)e] (@) Ma,0, (©) KsC104 (© CHCH.CH, (g) CHsCH,CHs (h) CH;COOH @ CH;COOH @)_ Cusd,.5H.0 20)" @) $205" (in) Nays (0) Natigo, 2) What is the oxidation number of nitrogen in the following compounds? @) NO; () N04 (@) No @ m0 (©) N20. () Ny (@) HNO, (s) HNO, (Hig), 80, 3) Which of the following are redox reactions? Where applicable, specify the oxidzing agent and the atom being oxidized in each case. @) Ni@ + 3H,(6) — 2NH@) (b) Zn(s) + Cu*(aq) —> Zn?*(aq) + Cu(s) (6) BaCis(aq) + 2ARNOs (@q) —> Ba(NO3)a(aq) + 2ARCI) (4) Cu(OH)s(6) + 4NH5(2q) —> [Cu(NHs js} (OH), (2a) (@) 2Na(s) + 2H,0(@) —— 2NaOH(@q) + Hs(@) (©) Zn(9) + HS04(aq) —> ZnSO, (aq) + Ha(@) (G) Cu(s) + 44NO5(aq) —> Cu(NO, ) (aq) + 2NO(@) + 24,008) (h) 3€u0G) + 2NH(@) —> 3CuG) + Na(G) * 3H0@) 1534) 5) 8) v 154 In which of the following reactions does Fe**(aq) act as (a) reducing agent (b) oxidizing agent? (i) Fe*"(aq) + Ma(s) — Fels) + Mz**(2q) Gi) 4Fe?Gaq) + $0," (aq) + 6H'(aq) —> 4Fe™(aq) + S16) +3H,0(8) (iii) Fe?"(aq) + 20H (aq) —> Fe(OH), (s) Explain whether iodine is oxidized or reduced in each of the following two half-reactions: @ Iy(aq) + 2° —> 2 (aq) Gi) 13(@q) + 1201 (aq) —* 2105 (aq) + 6H, 0(@) + 10e° Hence balance the following equation: 1y(aq) + OH"(@q) — Taq) + 103(aq) + H20@), Hydrogen peroxide reacts with acidified potassium iodide according to the following equation: H,02(aq) + 2KI(aq) + Ha$O«(aq) —* 2H20(8) + Ia(aq) + K2S04(aq) (@) State which reactant is reduced. (b) State which reactant is the reducing agent. (©) Write the oxidation half-equation. (@) Weite the reduction half-equation. (@) Calculate the mass of iodine liberated when 1.360 g of pure hhydrogen peroxide are added to an excess of potassium iodide solution acidified with difute sulphuric acid. Using the method of half-equations (involving ether ions and electrons or oxidation states, balance the following equations. (a) Cu(s) + H$04(@2) —> CuSO, (aq) + Hz O() + SO2(g) (b) Cr207*(@q) + $02(8)+ H"(aq) — Cr*"(aq) + $047 (aq)+Hs0(8) (©) Cu(s) + HNO, (aq) —> Cu(NOs (aq) +H,.0@) + NOG) (8) Cu(s) + HNOs aq) —> Cu(NOs)o (aq) + 12 (2) + NOB) (©) NOz(aq) + S05" (aq) + H"Gaq) — NOG) + S0,*(aq) #120) (9) Za(s) + HNOs(aq) —r Zn(NOs (aq) + NH NOs(@q) + H20(8) (@) NHy(@) + 03(@) —> NOG) + HO) (i) Mn04 (aq) + (aq) + Haq) — Ma*(aq) + 1n(2a) + HO (@)_ COs(aq) + Fe?"(@q) + H'(aq) — CI(aq) + Fe*"(aq) + H,0(8) G)_ NHy(g) + CuO() — Cus) + H, 0(@) + Nz) ) Fe (aq) + 802(@) + H.0@) —> Fe™(aq) + $0." (aa) + H'(a9) 8) Complete and balance the following equations: (Refer to the tables of common oxidizing agents and reducing agents if necessary.) (@) Ch(g) + Fe*(aq) — (@) MnO. (aq) + S*(aq) + H'(@q) — (©) C107?(aq) + (aq) + H"(aq) — 9) (@) Write a halfequation for the reduction of permanganate ion in acidic medium, (b) Write a half-equation for the oxidation of sulphite ion. (©) Hence write an ionic equation for the reaction between acidified potassium permanganate and sodium sulphite solution (@) What is the volume of 0.10 M KMnO, solution which would react exactly with 25 cm? of 0.10 M.Na3SOs solution? 10) When sulphur dioxide is passed into an aqueous solution of chlorine, the greenish-yellow colour of the chlorine water disappears. Which jon is being formed as sulphur dioxide reacts with water? Write the redox equation for the reaction which occurs between this fon and chlorine. 11) @) State the ion responsible for the colour of () iron(11) sulphate solution Gi) potassium permanganate solution, Give the colour of the ion in each case. (b) When aqueous solutions of iron({l) sulphate and acidified potassium permanganate are mixed, a pale yellow solution is formed. Explain this observation and give an ionic equation for the reaction that ocours. 155ELECTROCHEMICAL 1 1 SERIES & ITS APPLICATIONS ELECTROCHEMICAL SERIES Electrochemical Series (E.C.S.) of some systems Tonic halfequaton Reduction —————> bration riaiing agent Reducing agent very weak | K"(aq)+ e = Kis) Jvery strong oxidizing | Ca?"Gaq)* 26 2 aw) keducing xls | Ca "a9)2 > Nw sens Mg?"(aq) + 2c” = MgGs) AP "ag) + 3° = AIG) Za) + 26 > an 5 Pe(ag)+ 26 a) 5 Ble | roman e2e = mo gle 3\% 2H"(aq) + = He) 3 a Ele | Sograayeairag +2 SOni@+ 24,00 | 3/7 3|E | cvtaqys 20 = ae s|z 8]2 | O@)+2H,0@)+4e = 40H (aq) aig SB | kigeae = ren % z]p | rare = Fen aig E/E | Noags2ap+e = Novwr+How | 3/2 B/E | avaee Aa) Ae Bd 26 = Bren a Gig) +26 acres) very strong] MnOztaq)* BHY(ag) + Se Mn"taqyestt, 0) ery weak Dxidang | 8.06"(aq)> 26 250.9) reducing scents | Frye ze 2a) eens The Electrochemical Series (or Redox Series) provides a very clear basis for comparison of oxidizing or reducing power in aqueous solution. 156 ‘The position of any half-teaction in the series is given by the voltage cof a specially constructed electrochemical cell, (Detailed account of this is beyond the scope of our syllabus.) When using the ECS., we should remember that it is based on reactions occurring at 25°C and involving one molar solutions. The position of a halfequation in the series can alter if the conditions differ from these standards. Predictions from Electrochemical Series (1) Predicting strength of reducing agents and oxidizing agents ‘At the top of the E.CS., there are metals which are the strongest reducing agents and therefore their corresponding ions the weakest oxidizing agents. Conversely, at the bottom, there are nonmetals Which are the strongest oxidizing agents, therefore their corresponding ions the weakest reducing agents. This enables us to predict which substances will be capable of oxidizing or reducing others. (Gee Examples 11.1 and 11.2) (2) Predicting possibility of reactions ‘Two halfequations can be combined into a complete equation that represents @ possible reaction — the halfreaction lower in the ELS. will go as written, while the one higher will go in reverse. (See Examples 11.3 and 11.4) (3) Predicting feasibility of electrochemical cells ‘An electrochemical cell is a device in which chemical energy is converied into electrical energy (ie. electricity is generated as a result of chemical reaction), It has two electrodes — anode where ‘oxidation half-reaction takes place and cathode where reduction halfteaction takes place. (Remember the words red cat) The feasibility of an electrochemical cell can be predicted as in (2) by considering the corresponding two half-equations (Gee Examples 11.5 and 11.6) (4) Predicting discharge of ions in electrolysis In electrolysis, there may be more than one type of positive ions (or negative ions), but usually they are nor all discharged at the same time, It is possible to predict from the E.C.S. which fons ‘would be discharged in preference to others. (See discussion on p.166 and Examples 11.9 and 11.10) 187Example 11.1 (a) Arrange the following reducing agents in decreasing order of reducing Power in aqueous solution: Brag), Asts), Cals), Zins) (6) Arrange the following oxidizing agents in decreasing order of oxidizing ower in aqueous solution: Ms*(aq), Cig), — Brs(),—H"(aq) ‘The answers can be deduced from the positions of the elements or ions in the ECS, (@) CG), Zn(6),—AgG), Br (aa) ©) ChG@), Ba, Hea), Mea) Example 11.2 Refer to the E.CS, in answering the following questions. (a) Which of the following can oxidize Zn(s)? Meals), Me2"(aa), Cus), Cu"(aq) (b) Which of the following can reduce Zn*"(aq)? Mefs), Me™(aq), Cus), Cu*(aq) (c) Which of the following can be oxidized by Fe™/aq)? MnOstaq), CTfag), Ir(s), faq) (4) Which of the following can be reduced by Br (aq)? Chis), aa), Tals, (aq) ‘The positions in the E.C.S. provide a direct measure of the relative ‘oxidizing and reducing power of different species, In general, any oxidizing agent on the left will oxidize any reducing agent above it on the right: any reducing agent on the right will reduce any oxidizing agent below it on the left (@) Cua). (ote that Ma(s) and Cu(s) are not oxidizing agents; Mg*(aq), though an oxidiaing agent, is not strong enough to oxidize Zn(3).) (b) MeG), (Note that Me™(aq) and Cu*{aq) are not reducing agents; Cu(s), 158 though a reducing agent, is not strong enough to reduce Zn**(aq).) r@ | © [Noe mat Masa) and 16) ae ot edicing ages rea, though a reducing agent, is not strong enough to reduce Fe**(aq).) @) As) © (Note that CI(aq) and [(aq) are nor oxidizing agents; 13 (6), though an oxidizing agent, isnot strong enough to oxidize Br(aq).) Example 11.3 Combine the two half-equations in each case into an equation for 1 posible reaction (0) Mg*(aq) + 2& > Mss) Fe™(ag) + 2& © Fe(s) fo) AP"(aq) + 3e” © Alls) Cu (aq) + 2e + Cufs) (c) Ag (aq) + © = Asts) Qu*(aq) + 2 + Culs) (a) Pry) + 20° > 2Br (aa) hfe) + 2€ = 2Cr (ag) + 2*(aq) + 2e° = Mats) @ (will go in reverse: Mg(s) —> Mg**(aq) + 2€ Fe?(aq) + Mg(s) —* Fe(s) + Mg™(aq), which is the required (©) By similar reasoning as in (a), we have Als) —> Al™(aq) + 3e° @ cu (aq) + 26° —> Culs) @ (@) X2—-2AKG) — 2AN"(aq) + 66" (i) X 3 3Cu™(aq) + 6” — 3Cu@) Combining, . 2AlG) + 3Cu(aq) —> 2Al"(eq) + 3CuG) 159© Ag Ga) + — AgG) o Cu(s) — Cu*Gaq) + 20° ) @X2_-2Ag'(aq) + 2e° —> 2Ag(s) Combining, Cu(s) + 2Ag"(aq) —> Cu*(aq) + 2Ag(6) (@ 2Br (aq) — Br) + 26° @ Cla(g) + 2° — 2CT(aq) Gi) Combining, 2Br(aq) + Cla(g) — Bra@ + 2C1@q) Example 11.4 Predict, with reasons, whether there is a chemical reaction in each Of the following cases, (a) A copper coil is dipped in aqueous silver nitrate solution. (6) A small piece of silver is dropped into dilute sulphuric acid. (2) ‘There is a chemical reaction (redox reaction). Consider the 2 half-equations: CuGaq) + 2° + Cus) @ As‘(aq)+e = ARG) Oo) Stace Gt below () in the ECS 0 Gi) will proceed as written: Ag’(aq) +e” —> Ag(s); (©. will goin reverse: Cu(s) —> Cu*(aq) + 26° Thus the predicted reaction would be: Cu(s) + 2Ag"(aq) —> Cu™ (aa) + 2A0(6) (©) There is no reaction. Consider the 2 half-equations: As(aq) +e + Aats) © 2H'Gq) +2 Ha(g) (i Since () is below (i) in the E.C.S,,s0 @)_ will proceed as written: Ag‘(aq) +e” —> Ag(s) i) will go in reverse: Hy(g) —> 2H1"(aq) + 26° Therefore the only possible reaction would be: 2Ag"(aq) + Ha() —> 2Ag(6) + 2H"(eq) Thus there is no reaction between metallic silver and dilute acid. 160 Note: Theoretically, if hydrogen gas is bubbled through aqueous ‘Ag(l) solution, silver should be precipitated out and the solution should become acidic (due to H'(aq) ions formed), It happens that at room conditions, the rate of this reaction is too slow for any change to be observable. Example 11.5 It is given that the half-cell equation Is(aq) + 2€ * 2(ag) is positioned above Fe*(aq) + & * Fe™(aq) in the Electrochemical Series. (a) Aqueous solutions of iron(III) chloride and sodium iodide are mixed. (i) What do you observe? (i) Which is the oxidizing agent in the reaction? (iti) Which is the reducing agent in the reaction? (6) The above reaction may be carried out without directly mixing the solutions, as shown by the following setup, which is allowed to stand for ten minutes. illiammoter a Pr FeCl, aa) Nala) — ‘Alter paper soaked in NaCl solution (as slt bridge’) (i) What do you observe? (ii) The needle of the milliammeter deflects to give a reading. What does this indicate? (itt) Write half-equations for reactions occurring at electrodes A and B. Write an equation for the overall reaction. (iv) Which electrode is the anode? Why? (v) Which electrode is the cathode? Why? (vi) What is the direction of electron flow in the external circuit? (vit) Can the reaction occur if the ‘salt bridge’ is removed? Why? 161(@) (@ There is brown coloration in the resulting solution due to liberation of iodine () FG). Git) Tq). (©) (@ There is brown coloration around electrode A due to liberation of iodine (i) This indicates @ flow of electrons in the circuit, that is, an electrochemical cell has been set up. (iil) AtA:21(@q) — I (aq) + 2e"sat B: Fe™(aq) + &° — Fe™(aq); ‘overall: 2Fe™(aq) + 2(aq) —> 2Fe?"(aq) + I3(aq) iv) A is the anode because oxidation takes place there (¥) B is the cathode because reduction takes place there (vi) Electrons flow from A to B in the external circuit (vii) No. This is because there will then be no electrical connection between the two half-cell Note: In an electrochemical cell, the anode is the negative electrode (or pole), while the cathode is the positive electrode (or pole) electron flow Example 11.6 1 __f porous pot 20804(29) |_copper ‘container = CuS04(aq) 162 The above diagram shows a setup for a simple electrochemical cell — the Daniell cell. (a) Write a half-equation for the halfreaction at the copper container. (b) Write a half-equation for the half-reaction at the zinc rod. (c) What is the direction of electron flow in the extemal circuit? (d) Which is the positive pole of the cell, copper or zinc? (e), What is the function of the porous pot in the setup? (a) At Cu: Cu(aq) + 2° —+ Cubs) (b) At Zn: Zn(s) —> Zn*(aq) + 2e (©) From Zn to Cu. (@) Copper. (€) It allows electrical contact between the two half-cell, yet prevents the direct contact of Zn(s) and CuSO«(aq). ELECTROLYSIS Defining some terms ‘An electric current is 2 flow of electrons, ‘A metallic conductor is an element which conducts electricity in both solid and molten state, but which is not chemically changed by the electricity. (Note that all metals belong to this class. Carbon in the form of graphite is @ non-metal but behaves like metallic conductor.) ‘An electrolytic conductor or electrolyte is a compound which, when in aqueous solution or molten state, conducts an electric current, such ‘conduction being always accompanied by chemical decomposition, A nonelectrolyte is a compound which is not an electrolyte. Electrolysis is the decomposition of an electrolyte by passing an lectrie current through it. A voltameter is a vessel in which electrolysis takes place, ‘The electrodes are conductors by which an electric current (or electrons) enters and leaves an electrolyte. The electrodes are usually solid metals or graphite. (In some cases, liquid mercury may be used.) ‘The cathode is the negative electrode by which electrons enter an electrolyte and where reduction occurs. ‘The anode is the positive electrode by which electrons leave an electrolyte and where oxidation occurs. 163Explanation of electrolysis by ionic theory To explain electrolysis by ionic theory, let us consider the electrolysis of a molten electrolyte X°Y™ = direction of electron flow I electric curent power conducted by anode $f) source ode ‘elocilized electrons | ane re er conducted by (anion) ation) | — votuaneter mmobiieions {electrolytic cell) Diagram showing the procest of electrolysis (1) Conduction of electric current by electrolytes In metallic conductors, an electric current is conducted by delocalized electrons in the metals. In case of electrolytes, however, it is conducted by migration of mobile ions, (2) Decomposition of electrolytes by electric current During electrolysis, cations (positively charged ions) are attracted to cathode and anions (negatively charged ions) to anode. At cathode, cations are reduced by gaining electrons which they are deficient of. At anode, anions are oxidized by losing their excess electrons. (If the anode is not inert, there may be some other possible reactions, as illustrated in Example 11.9.) Thus both cations ‘and anions lose their charges, ie. they are discharged to become neutral atoms or radicals, which may combine with one another to give more stable particles. Thus the electrolyte is electrically decomposed. To illustrate the aforesaid, take the electrolysis of molten sodium chloride as example, At cathode: Na‘(l) + &° —+ Na(®) (seduction) At anode: 2C1(@) —* Clh(g) + 2e° (oxidation) The overall reaction is 2Na"(®) + 2CI() —+ 2Nal®) + Clee) 164 Note: In electrolysis, a dc. (ditect current) power supply must be used. ‘An ac. (alternating current) power supply should not be used, otherwise there would be no fixed cathode and anode. Example 11.7 Consider the following substances: (1) Mercury (2) Molten sulphur (3) Tetrachloromethane (4) Solid potassium bromide (5) Molten lead{tl) iodide (6) Pure sulphuric acid (7) Dilute sulphuric acid (8) Solid graphite (9) Aqueous magnesium sulphate (a) Classify each of these substances in one of the following three way's ‘according to its behaviour to a direct current: (i) Non-conductor (ii) Conductor, with chemical changes taking place (iti) Conductor, without chemical changes taking place. (0) For each of the above substances which are conductors, state the particles responsible for the conduction of electricity fe} Explain any difference in behaviour of pure sulphuric acid and ditute sulphuric acid towards a direct current (@) @ Noveonductor of electricity: rolten sulphur, tetrachloromethane, solid potassium bromide, pure sulphuric acid (ii) Conductor, with chemical changes taking place: ‘alten lead(II) iodide, dilute sulphuric acid, aqueous magnesium sulphate ii) Conductor, without chemical changes taking place: mercury, solid graphite (b) Molten lead(I) iodide: mobile Pb**() and I(@) ions; dilute salphuric acid: mobile (aq), OH(eq),HSO, (aq), SOs” (aq) fons; Aqueous magnesium sulphate: mobile Mg”*(aq), SO? (aq), (aq), OF (aq) ions; mercury: delocalized electrons; solid graphite: delocalized electrons. (©) Pure sulphuric acid is a simple molecular compound containing no ions, thus it does not conduct electricity. But when it is mixed 165with water to give dilute sulphuric acid, mobile ions are formed according to the following reactions: H,SO4(®) + water —> H'(aq) + HSO, (aq); HSO,(aq) + water —> Haq) + $0." (aq); H,0(@ + H'(aq) + OH(aq) Preferential discharge of ions Factors which affect preferential discharge of ions are: (1) Position in the Electrochemical Series Position of an ion in the E.CS. often decides its preference to be discharged. . Kw a Nat My ay stronger increasing Zn" > cations migrate to cathode | oxidizing ease of Fe* agents discharge Po w r - stronger | increasing % | nine migatetoanoie | teams |} surat e cee || ochre so.” 2) Concentration ‘An ion present at a low concentration is more difficult to discharge than the same ion at a high concentration. Let us consider the example of electrolysis of molar sodium chloride solution. From the positions in the E.CS., OH ions should be discharged in preference to CI ions. However, the CI’ ions (I M) are far more ‘numerous than the OH” ions (only ~ 107 M), thus the reaction 166 2CT(aq) — Cha(g) + 2° proceeds in preference to 40H (aq) — 2H20(@) + 02(g) + 4e° (3) Nature of electrode The nature of electrode may also affect the preferential discharge of ions. For example, the electrolysis of sodium chloride solution using inert electrodes (such as platinum or carbon) gives hydrogen at cathode. Here the position of H” is well below Na’ in the E.CS., tnd the concentration effect does not reverse the expected order of discharge as in the example mentioned in (2) above. However, if mercury is used as cathode, sodium metal, and not hydrogen gas, is formed. (The reason for this is too complicated to be considered here.) Therefore change of electrode results in a different product in this particular case. Example 11.8 A small crystal of copper(ll) sulphate-S-water was placed at the centre of a strip of filter paper moistened with tap water. The strip was held on a microscope slide by crocodile clips which are joined to 4 20-v0lt dc. supply. wet crystal of, Ter paper CuSO,.SH,O microscope ‘lide 20V de. supply (a) Make a sketch to show position of any coloured patch which would be expected to develop on the filter paper within several minutes. What ion was responsible for the coloured patch? (6) List the ions which had moved towards the positive electrode. 167(c) List the ions which had moved towards the negative electrode. (d) If the experiment was repeated with a small crystal of potassium ermanganate instead of the copper{Il) sulphate-S-water crystal, what would you expect to see? @) ‘original spot ‘of C4S0,.5H20 ‘ue patch LZ] Cu" (aq) ion was responsible for the blue patch (©) Tons moving towards the positive electrode: $0,*"(eq), OH (aq). (©) Ions moving towards the negative electrode: Cu*(aq), H'(aq). (@ A purple patch (due to MnO,(aq) ion) would be seen near the positive electrode (ie. near A), Example 11.9 In the electrolysis of copper(II) sulphate solution using pure copper electrodes, predict the half-reactions at the electrodes by making use of the Electrochemical Series. The ions present are Cu*(aq), _$0.*(aq), H'(aq),__ OH{aq). from CuSO, from slight ionization of water At cathode, reduction takes place. Both Cu**(aq) and H’(aq) migrate to cathode. Cu (aq) is lower than H'(aq) in the E.CS., so Cu*(aq) ions are preferentially discharged. ‘Cu*(aq) + 2e° —> Culs) (copper deposits on cathode) At anode, oxidation takes place. 168 ‘There are three possible oxidation reactions: 1) Discharge of OH"(aq) ions 2), Discharge of $0,*(aq) ions 3) Removal of electrons from Cu atoms in the anode, releasing Cu®*(aq) ions into solution. ‘As can be seen from the Electrochemical Series, Cu(6) is a better reducing agent than OH{@q) and SO,*(aq). Thus Cu is oxidized as follows: Cu) — Cu(aq) +2” (copper anode dissolves) (This process requires less energy than needed for discharge of OH (aq) ions or $O,*(aq) ions.) Example 11.10 Impure copper (containing zinc, lead and silver as impurities) is refined by electrolysis, using a set-up as follows: de. source impure copper_| ‘ure copper as athode ss anode Cus04(09) Describe reactions taking place at the electrodes, Using similar reasoning as in Example 11.9, we have: at anode, the reaction Zn(s) —+ Zn?*(aq) + 2€° takes place first, then Pb(s) —> Pb*(aq) + 2", and lastly, Cu(s) —> Cu™(aq) + 26° (Copper dissolves from anode) Silver metal falls and forms a sludge at the bottom of the vessel. (ote: (i) The reaction Ag(s) —> Ag'(aq) + €° does not take place. (i) There is a white precipitate of PbSO, due to Pb**(aq) + $0." (aq) —> PbSO.(6)) 169at cathode, ‘Cu*(aq) ions are preferentially discharged because they ate a better oxidizing agent than H'(aq) ions and also the Zn™(aq) ions given from anode. Cu"(aq) + 2° —> Culs) (copper deposits on cathode) QUANTITY OF ELECTRICITY If a current of 1 ampere flows through a conductor for 1 second, the quantity of electricity passed is 1 coulomb. ‘Thus quantity of electricity(Q) = current(l) X _time(t) in coulomb(C) in ampere(A) in second) A FARADAY AS ONE MOLE OF ELECTRONS ‘The charge of a single electron has been found to be 1.602 X 10°'°C. 1 mole of electrons contains L (6.023 X 10*) electrons, which therefore have @ total charge of (1.602 x 10°!) x (6.023 X 10) = 96 500 C ‘This quantity of electricity is commonly known as 1 faraday(F). Charge of 1 mole of electrons = 1 F = 96 500 C ‘The value 96 500 mol“! is called Faraday Constant. Example 11.11 Find the quantity of electricity (in faradays) required to liberate 2 moles of aluminium (Al) from a molten solution of aluminium salt. APM@ + 3 — AIG) mole 3 moles 1 mole 1 2 moles Quantity of electricity required = 2X 3 = 6 moles of 6F Example 11.12 In an experiment to determine Avogadro Number L by electrolysis, 1156 coulombs liberated 0.381 g of copper from copper(II) sulphate solution. What is the value of L? (Charge of an electron = 1.60 X 10°? C; Ay of Cu = 63.5) 170 No. of moles of Cu liberated = —#st ‘molar mass = 0381 a = Be = 600x 10 Halfequs is: Cu?"(aq) + 26° —> Cu(s) 2moles 1 mole no. of moles of Cu liberated X 2 6.00 X 10? x 2 = 120X107 No. of moles of electrons passe Quantity of electricity passed = no. of moles of electrons X L X charge of an electron = 11s6¢ 1.20 X 10? X LX 1.60 x 107? = 1156 1156 a 1 ROK TOT 1.6K 177 ~ 602 * 10% mot Faraday’s Laws of Electrolysis FARADAY’S FIRST LAW OF ELECTROLYSIS states that the mass ‘of a substance liberated at (or dissolved from) an electrode during electrolysis is directly proportional to the quantity of electricity passed through the electrolyte. Example 11.13 A current of 0.45 A flowing for 25 minutes liberates 0.15 g of a metal M, What mass of M would ‘be liberated by a current of 0.25 A passing for 36 minutes? Let the unknown mass be x g By applying Faraday's Fiest Law of Electrolysis, 0.18 _ 045 x QS X 60) x” 025. (36 X 60) = x = 012 ‘That is, 0.12 g of Af would be liberated. FARADAY'S SECOND LAW OF ELECTROLYSIS states that the umber of moles of different ions discharged by the same quantity of electricity is inversely proportional to their respective ionic charges. imExample 11.14 ‘An electric current is passed through two electrolytic cells fitted with carbon electrodes and connected in series. If 2.54 g of copper are deposited on the cathode of the cell containing copper(II) sulphate solution, find mass of silver deposited on the cathode of the other cell containing silver nitrate solution. ‘Since the two cells are connected in series, the same quantity of electricity is passed through each of them. _ 254 _ No. of moles of copper deposited = 2>>-= 0.0400 No. of moles of copper(I) ions discharged = 0.0400 By applying Faraday's Second Law of Electrolysis: no. of moles of copper(I) ions discharged _ _charge on silver fon ‘io_of moles of silver ions discharged ~ charge on copper(II)ion i 2 No. of moles of silver ions discharged = 0.0400 X 2 = 0.0800 No. of moles of silver atoms deposited = 0.0800 Molar mass of silver = 108 g Mass of silver deposited = 0.0800 X 108 = 8.648 ‘When working on calculations in electrolysis, we usually do nor apply Faraday's Laws of Electrolysis directly. Instead we base our calculations on first principles, using the mole concept (1) Write down the ionic halfequations for the halfteactions at the electrodes concerned. (2) Write undemeath the half-equations the involved quantities in moles. (3) Work out the required answer by simple proportions. Study the following examples. Example 11.15 Caleulate the mass of aluminium that would be deposited on cathode during the electrolysis of a molten solution of an aluminium salt, by a current of 9.65 amperes flowing for an hour. Quantity of electricity passed = current in amperes X time in seconds = 9.65 X (60 X 60) = 34740C nm = ay of sty a covlni Wo. sie etn aed = of ey sa1u0 = HHO. 930 Uatsacton at xe AI") + 3° —> AIG) mots le nce 3 molt feos Iwate 1 mol of A, 0360 mole af evens theres 1 x 222 or 0120 mole of A Molar mass of Al = 27 g. Mass of Al deposited = 0.120 X 27 = 3.24 g Example 11.16 What current in amperes will deposit 6.35 g of copper in 10 minutes rom a copper(it) solution? Number of moles of Cu deposited = 253 = 0.100 [At the cathode: Cu**(aq) + 2e° —> Cu(s) 2moles 1 mole Since 2 moles of electrons liberate 1 mole of Cu, ‘no. of moles of electrons that liberates 0.100 mole of Cu = 0.100 X 2 = 0.200 Quantity of electricity = 0.200 x 96500 = 19300 C Q _ 19300 Tet" Tox 60 322A Example 11.17 What mass of copper would be deposited by the quantity of electricity that liberates 2.24 dim* of oxygen measured ats...” 40H (aq) —> O2(8) + 2H, 0(8) + 40° I mole 4 moles 24 24 Number of moles of O, liberated = 0.100 173[Number of moles of electrons required = 0.100 X 4= 0.400 cu (ag) + 26 —— cul, 2moles I mole 0.400 mole - Namber of moles of Cu deposited = 0400 x 5 = 0200 Molar mass of Cu = 63.5 g Mass of Cu deposited = 0.200 X 635 = 127g Example 11.18 A current of 2 A was passed for 1 hour 37 minutes and 30 seconds through a molten solution of a salt of a metal M. 2.10 g of metal M were deposited on the cathode. (A, of M = 52.0) (a) Find the number of positive charges carried by one ion of M. (b) Write a half-equation for the liberation of M at the cathode, (2) BE (+ ne” — Mos) 2.10 320 2X (1 X 3600 + 37 X 60 + 30) 11 700 € Number of moles of M deposited 0.0404 Quantity of electricity passed 11700 = Se309 7 O21 F Number of moles of electrons required to liberate 1 mole of M Soin 0.0404 Number of +¥e charges carried by one ion of M = 3 () M@) + 3° —+ ME) Example 11.19 An electrical cireuit is set up as shown below. X and Y are silver electrodes while Q and R are copper electrodes, 174 2 6V de. source “ FG HEE aa ‘oltameter A vollameter B On passing a current of 0.45 A for 30 minutes, 0.906 g of @ substance is liberated at Y. Initially, gas bubbles are liberated at R, but there is no observable change at Q. However, after a short time, the solution around Q becomes noticeably blue in colour. (a) Indicate polarity of electrodes X, Y, Q and R. Is ¥ the anode or cathode in voltameter A? (0) Write a half-equation for the halfreaction at Y. (e) How many moles of atoms are liberated at Y? (d) How many moles of electrons must have flowed through the circuit when the number of moles of atoms in (c) is liberated at Y? (e) How many coulombs of electricity flow through the circuit during the experiment? (f) Hence calculate the quantity of electric charge carried by 1 mole of electrons. What is the value of the Faraday Constant? (s) Write halfequations to represent the initial changes taking place at the electrodes of voliameter B. (h) Explain the blue coloration observed around Q after some time. (i) What will be observed at R when the experiment has continued for a considerable length of time? Explain. @ Xt GY G+ SRK Y is cathode. (b) Ag‘(aq) + & —> Ag(s) 175mass _ 0.906 ‘molar mass ~~ 108 = 839X 10? (©) No. of moles of Ag liberated = (@) From (b), no. of moles of electrons passed = no. of moles of Ag liberated 8.39 X 10? (€) Quantity of electricity passed = 0.45 X (30 X 60) = 810 (From (A) and (@), 8.39 X 10? mole of electrons carries a charge of 810 C, hence 1 mole of electrons would carry a charge of 810 , B39 x 197 ~ 965 X 10" C Faraday Constant = 9.65 X 10C mol @ At Q (anode): Culs) —+ Cu"(aq) + 26° ote: This, half-eaction takes place in preference to discharge of OH (aq) and $0," (aq) ions) At R (cathode): 2H"(aq) + 2e°—> H2() (1) Due to Cu*(aq) ions formed from copper anode. (A reddish brown deposit of copper will be observed at R. Cu?" (aq) ions formed from anode are discharged in preference to Haq). Example 11.20 An electrical circuit is set up as shown below. The four electrodes P,Q, Rand $ are made of carbon. 5M sodium chloride solution Fitmas theostat 176 (@) No current flows while the potassium iodide is in the solid state, but the bulb lights up when water is added, Explain why this ‘happens. (b) What is seen around electrode R after the current flows for a while? Give the ionic equation, (c) What gases are collected in the tubes above electrodes P and Q respectively? What is the volume ratio of these two gases? Give ionic equations for the reactions occurring at electrodes P and (. (d) What is the colour change of the litmus during the electrolysis of the sodium chloride solution? Explain why this happens, (e) A current of 0.1 ampere is passed for 20 minutes. (i) How many coulombs of electricity have passed? (ii) How many moles of the gas have been collected in the tube above electrode P? (1 faraday = 96 500 coulombs) (iii) What volume of the gas has been collected in the tube above electrode Q at room temperature? (Molar volume at room temperature can be taken as 24 dm?) (1) Why is the sodium ion of the sodium chloride solution not discharged? (HKCEE) (@) Potassium iodide is an electrolyte but not a metallic conductor. Solid potassium iodide does not conduct electricity because its ions are not mobile (the ions are held strongly together by ionic bonds), However, an aqueous solution of potassium iodide will conduct electricity because then the ions are mobile. (>) A brown coloration is seen around R (due to iodine liberated) 20(aq) — Iy(aq) + 26° (©) At P, chlorine is collected, At Q, hydrogen is collected. ‘The volume ratio of chlorine to hydrogen collected is 1: 1. AUP, 2CV(aq) — CG) + 26° (ote: Cl(aq) is discharged in preference to OH'(aq) because of the concentration effect.) At Q, 2H"(aq) + 2° —> Ha) 7(@) AtP: ted coloration. (Note: This is due to acids formed when some of the liberated chlorine gas dissolves in water); [At Q: blue coloration. (Note: H'(aq) is discharged, leaving an excess of OH(@q)) ‘After a while, the solution tums colourless due to bleaching action of chlorine, ©) @ Quanity of electricity passed = 1X t = 0.1 X (20 X 60) = 120€ (i) Ae, 20(aq) — Chie) + 28 Tmole 2 moles lt mole 96500 Number of moles of Cl; gas collected 120 - 4 se500 XZ * 622% 10 (ii) From (c) and @) (ii), no. of moles of Hz liberated at Q = no. of moles of Cl; liberated at P = 6.22 X 10% Volume of Hy collected at Q at room temperature = 622 X 10" X 24 dm? = 0015 dm? = 15 cm® (9) Na'(aq) is & much weaker oxidizing agent than H(aq) ‘The half-equation Na‘(aq) + e” = Na(s) is well above 2H (aq) + 2€° * Ha(G) in the Electrochemical Series. RUSTING OF IRON Corrosion of a metal is its gradual deterioration due to reaction with air, water or other chemicals to form oxides or other compounds. ‘The corrosion of iron is called rusting, Conditions for rusting Rusting requires the presence of both oxygen and water 78 Rusting is an electrochemical process Rusting of a single piece of iron Consider a piece of iron exposed to open atmosphere. The metal soon becomes moist. The process of rusting involves the following steps: (anodic area) izon 1. Oxidation at anode: Fe(s) —> Fe®"(aq) + 20° The electrons are transferred to oxygen and water molecules. 2. Reduction at cathode O2(g) + 2H,0(8) + 4e”— 40H (@q) Note: Here the anode (or anodic area) is the region on the iron surface where concentration of dissolved oxygen is low; cathode (or cathodic area) is the region of higher oxygen concentration. The part forming anode is corroding. 3. Formation of Fe(OH); and then Fe(OH), Fe?(aq) + 20H (aq) — Fe(OH),(s) 4Fe(OH)a(6) + O2(g) + 2H,0(2) —> 4Fe(OH),(6) 4. Slow formation of Fez 0y.xH,0 from Fe(OH)s. (Overall reaction: 4Fo(s)+ 303(@)+ 2xH,0(®) —+ 2Fe;0s.xH20(6) Rust is Fe,05.xH,0, a reddish brown solid. It is porous and does not form a protective layer, thus rusting continues until the iron piece corrodes completely. Factors that speed up rusting Iron rusts faster (1) in the presence of electrolytes, eg. acids, salts (2) at a higher temperature 179(3) when in contact with another metal lower than it in the E.CS. (An electrochemical cell is set up, in which iron is the anode and the other metal is the cathode.) Prevention of rusting Common methods to prevent rusting are: (1) Applying a protective layer on the iron surface, eg. painting (2) Using alloys of iron, e.g. chromium can be alloyed with iron to make stainless steel. (3) Sacrificial protection ‘The iron object is coated with or attached to a metal above iron in the ECS. (For example, in galvanizing, iron is coated with f thin layer of zinc.) The metal acts as anode (therefore it corrodes) while iron serves as cathode, Example 11.21 ‘There are three bright iron nails numbered 1, 2 and 3. A narrow strip of copper is wrapped round part of nail 2, and a strip of magnesium round rail 3. head copper strip magnesium He tp sail a2 vad These 3 nails are separately placed in Petri dishes containing an agaragar solution of potasium hexacyanoferateti!), phenolphthalein and sodium chloride, They are left to stand for an hour. (a), What isthe purpose of using potassium hexacyanoferate Il)? (b) What is the purpose of using phenolphihalein? (c) What would be observed around nail 1? {d) What would be observed around rail 2? What is corroding? {e) What would be observed around nail 3? What is corroding? (f) Compare rate of rusting in nails 1, 2 and 3. Hence suggest a method 10 prevent rusting. po (@) Hexacyznoferrate(II1) ions react with iron(II) ions to form a deep blue coloration (Turnbull's blue). Thus a blue colour indicates the start of corrosion around some region in iron which is acting as anode. (b) Phenolphthalein gives a pink colour in the presence of excess hydroxite ions, indicating a cathode. (©) Blue colour around head and tip and pink colour around shank of nail. (Deformed region of an iron piece usually behaves as anode because it is easier for metal atoms to be removed from there as positive ions.) (@) Pink cclour around copper and blue colour around iron. Iron is corroding, (©) Pink colour around iron and colourless gas bubbles trapped in the sagar-agar. Magnesium is corroding. (© Nail 2 musts faster than nail 1; nail 3 is prevented from rusting by sacrificial protection from magnesium. Rusting of iron can be prevented by connection to a metal higher than iron in the E.C.S. EXERCISE 11 1) By referring to the Electrochemical Series, choose among the following species: K'(aq), K(S), Fe™(aq), Fe*(aq), Fe(s), Fa(@), Faq), He(g), Ne(g) (a) thos: which can be classified as oxidizing agent only (b) thoe which can be classified as reducing agent only (©) thoe which can be classified both as oxidizing agent and reducing agent (@) thow which can neither act as oxidizing agent nor reducing agent (Assume that iron can exist only in oxidation states of 0, I and mm) 2) Combine the two half-equations in each case into an equation that would taze place, (@) Zn?"(aq) + 2e" * Zn(s) Cu(aq) + 22° ¥ CuGs) 181(©) Ch@) + 26° = 20g) 16) + 26 + 219) (c) Fe™"(aq)+ 2e° * Fe(s) AP*(aq)+ 3e° = Al(s) 43) Predict whether there is 2 chemical reaction in each of the following cases. Give brief reasons. (a) Dilute hydrochloric acid is added toa piece of zine (6) Magnesium powder and iron powder are mixed. (6) Zine powder is added to iron( It) sulphate solution, (@) Iron powder is added to zine sulphate solution 4) Potassium permanganate and potassium dichromate can both act as strong oxidizing agents in acidic medium. By referring to the Blectrochemical Series, suggest whether (a) hydrochloric acid (HCD) could be used to acidify (i) KMnOs Gi) K;Cr207 solution (b) hydrobromie acid (HBF) could be used to acidify (2) KMnOs Gil) KzCr207 solution in redox titrations. (Assume the acids and oxidizing agents to be 1 M in concentration.) 5) When the bare ends of two wires from the terminals of a battery are held near one another on a piece of red litmus paper, which has been moistened with concentrated sodium chloride solution, the paper is bleached at one wire and tums blue at the other. Explain these observations. 6) Give explanations for the following experimental observations: (@) When & voltage is applied between two electrodes touching 2 piece of moist starchspotassium iodide paper, a blue colour appears in the paper around the anode. (b) When carbon electrodes L and R are put into molten lead(tt) bromide, as shown in the figure below, the electric bulb lights up and brown fumes are observed around electrode L. When the bumer is removed, the light of the electric bulb gradually goes out. 182 carbon electrodes ‘molten lead) bromide oo 7) (a) A_ moderately concentrated aqueous solution of copper(Il) sulphate is clectrolysed. The cathode is pure copper while the anode is copper contaminated with a small amount of zinc, icon, lead and silver. With the help of ionic equation, explain what happens ({) at the anode (ii) at the cathode (ii) in the solution when an electric current is passed between the electrodes. (HKCEE) (>) How many grams of copper will be deposited in one hour by a current of 2 amperes? (HKCEE) 8) How many faradays of electricity are required to liberate the following quantities of elements in electrolysis? (a) 0.1 mole of calcium (b) 1.204 X 107* aluminium atoms (c) 3 moles of oxygen molecules (@) 23 g of sodium (©) 2.24 dm? of chlorine at stp. 9) Find (a) number of moles and (b) mass of silver deposited in a silver- plating bath by passing a current of 1.5 A for 1.5 hous. 10) How many hours will it take for a current of 1.5 A to deposit 0.80 g ‘of metallic copper from a solution of copper(II) sulphate? 11) If 1 mole of electrons passes through dilute sulphuric acid during electrolysis, what volume of hydrogen gas at 25°C and 760 mm Hg ‘would be liberated at cathode? 18312) When an aqueous solution of sodium hydroxide is electrolysed using platinum electrodes, the hydroxide ions are discharged at the anode to give oxygen according to the following half-equation 40H (aq) —+ 2H20(®) + 02(g) + 4e° Ifa current of 25 Ais passed for 15 minutes, (a) how many moles of OH ions are discharged? (b) how many moles of oxygen (Oz) are produced? (©) what is the volume of this oxygen at s.tp.? 13) A direct current was passed through dilute sulphuric acid using platinum electrodes. (@) If 1 faraday of electricity was passed, calculate the number of moles of hydrogen and oxygen formed and the volumes they would occupy at stp. (b) What would be the volumes of gases if only 0.01 faraday was used? (©) What time would it take to pass 0.01 faraday if a current of 0.5 ampere was used? 14) What mass of copper will be liberated from a copper sulphate solution by a quantity of electricity that sets free 2 grams of oxygen? (HKCEE) 15) What total volume of gas, measured at s.tp., would be liberated from dilute sulphuric acid by the current which, flowing for the same time, deposits 0.635 g of copper from copper(II) sulphate solution? 16) A direct current is passed between platinum plates through solutions of copper(I) sulphate, ser nitrate and dilute sulphuric acid connected in series. If 0.210 g of copper is deposited in the first cell, calculate (@) the mass of silver separated from the second solution (b) the volume of hydrogen, measyred at room conditions, which is liberated from the third solution. 17) If the cost of electricity to produce magnesium is $x per kg of the metal, what is the cost of electricity for producing y kg of aluminium at the same rates? 18) The quantity of electricity which deposits 0.3 mole of silver can deposit 4.5 g of the metal scandium (symbol Sc, atomic mass 45), 184 a If the symbol for silver ion is Ag’, what is the symbol for scandium 19) A current of 3.86 A was passed for 1000 s through an aqueous solution of a salt of a metal M The mass of M deposited on the cathode is 2.24. (a) How many coulombs of electricity were passed in the experiment described? (b) If the atomic mass of M is 112, how many moles of atoms of M are present in 2.24 g of M? (©) How many (i) coulombs (ii) faradays of electricity would be needed to deposit 1 mole of atoms of M? (d) How many charges are carried by an ion of M? (©) Write 2 halfequation to show what happens to an ion of M when it is discharged at the cathode. 20) An element X has a molar mass of 88 g. When a current of 0.5 A was passed for 965 s, 0.22 g of X was deposited on the cathode. (@) Calculate the number of faradays of electricity needed to liberate I mole of X atoms. (b) Write the formula for the ion of X. (©) Write the formula for the hydroxide of X. 21) A molten compound containing Ni°* ions was electrolysed by a current of | ampere. After 2 hours and 40 minutes, 2.92 g of nickel were deposited on the cathode. Calculate the relative atomic mass of nickel. 22) The same current is passed through copper(II) sulphate solution for 90 minutes and another solution containing a metal ion M?* for 60 minutes. 0.8884 g of copper and 0.2238 g of M were liberated respectively. Calculate the relative atomic mass of metal M. 23) An aqueous solution of sodium ethanoate (CHsCOO'Na’) was electrolysed. The halfxeactions which occur at the electrodes may be represented by the following half-equations: cathode : 2H"@q) + 2e° —> Ha(g) anode: 2CH,COO'(aq) —> Cs He (8) + 2C0.(8) + 26° (2) What were the relative volumes of the gases collected at the cathode and anode respectively? (The solubility of carbon dioxide in water may be neglected.) 18524) 186 (b) After passing the gas collected at anode through concentrated sodium hydroxide solution, ethane (C;Hg) was collected and its volume was measured. This was found to be 25 em? (corrected to stip). How many faradays of electricity had been pasted through the sodium ethanoate solution? (©) What volume (corrected to stp.) of (i) hydrogen (i) carbon dioxide was also produced during the electrolysis? cals Electrodes: copper Solution: 0.1 M copper(l) sulphate Solution: 0.1 M sulphuric acid Electrodes: platinum ‘The diagram shows a circuit for the electrolysis of 0.1 M copper(II) sulphate solution and 0.1 M sulphuric acid in series. A steady current is passing through the circuit, (a) Write ionic equations for the reactions taking place at electrodes K,L,MandN, (b) What would be observed in cell B if the electrodes M and WV were moved closer together? (©) List three factors which could increase the rate of electrolysis in cell (@) How long would a current of 1 ampere need to pass in cell A before 0.0635 g of copper were deposited” (©) What would be the volume of hydrogen liberated at sip. in cell Bin the sare Cie with the saune eustent? quKere) 25) A compound X was found to conduct electricity when molten but ot when solid, After the passage of an electric current in molten X for some time, a metal which would mark paper when solidified was formed at one of the electrodes. At the other electrode, a violet vapour was evolved. The metal was removed, reheated in air in a crucible and kept molten for several minutes. On cooling, a yellow solid was formed. (a) What was the violet vapour liberated? (b) At which electrode would it be formed? (©) What is compound X? (d) Name the yellow substance formed by heating the metal in air. (e) Compound X was found to dissolve in boiling water. On cooling the solution, golden yellow shiny crystals were seen to form. Comment on the solubility of X in water. (0) X was again dissolved in boiling water and a piece of zine foil ‘added, what would be observed? Write an ionic equation for the reaction that takes place. 26) An electrolysis experiment was carried out using the circuit shown below. — sraphite ecttodes potassium iodide Solution rotten potassium ° iodide (a) It was noticed that the bulb lit up only when the potassium iodide in P had melted, and not before. Explain. (b) A colour appeared round the anode in each beaker, What was being formed? 1872) 188 (e) A metal which rapidly tarnished was formed at the cathode in P. What is it? (@) A gas was formed atthe cathode in Q. What is it? (©) Explain the formation ofthe gas mentioned in (4) (© A-ccurrent of 0.1 A was passed for 16 minutes. How many faradays of electricity is this? (a) 12 em? of gas were produced at the cathode in Q. How many ‘moles is this? (8) Comment on the results from (f) and (g) () the experiment was performed under a pressure of | atmosphere, then what was the temperature? ‘The apparatus shown in the diagram below was set up. x y platinum, {platinum electrode ectrode iute ditute ‘ulphurie Sulphuric aid acid copper) dichromate solution (a) Name the gas you would expect to be given off (i) at X (ji) at ¥. (b) After 30 minutes it was noted that colours had spread into the dilute sulphuric acid at A and B. Explain what colour you would expect to find in each limb. (©) The current was left on overnight in an attempt to increase the spread of colour. Next_morning a reddish-brown solid. was noticed on the negative electrode, Y. What is this reddish-brown solid likely to be? Explain how it may have been formed. (CDC. Sample Question) 28) An electric current is passed for some time through two voltameters connected in series. The first voltameter contains a concentrated solution of potassium chloride and the second contains a solution of copper(I) nitrate. The electrodes used are all platinum electrodes. It is found that 200 cm? of 0.200 M sulphuric acid are required to neutralize completely the potassium hydroxide formed in the first voltameter. (@) Find number of moles of hydroxide ions formed in the first voltameter. (b) Find number of moles of hydrogen ions discharged in the first voltameter. (©) Find number of moles of electrons required to discharge this amount of hydrogen ions. (@) Find () number of moles (ii) mass of copper liberated in the second voltameter, 29) {i spn 100 cm? of 100 em? of [_ 2M XS0. (09) ‘AgNOs(29) Gala cae The above diagram shows a circuit for the electrolysis of XSO4(aq) and AgNOs(aq) in series. (X is a metal less electropositive than hydrogen.) M,N, P and Q are platinum electrodes. The current is initially passed for a period of time such that 0.183 g of X is deposited on N and 0.622 g of silver on Q. The current is then passed for a further period of time until all the metal X is deposited in cell A, as indicated by constant weighing of WN. The total increase in the mass of Nin cell A is 2.558 (2) Explain the reactions taking place in cells A and B. (b) Calculate the molarity of the (i) hydrogen ion (ji) sulphuric acid 189which is produced in cell A after all the metal X has been deposited. (You may assume that the volume of solution in cell A remains unchanged.) 30) The following table gives some information about two elements X and ¥. Relative atomic mass_| Position in the Periodic Table x 39.1 Group 1 my 243 Group IL Same number of moles of two chlorides formed from X and Y are ‘mixed together and melted. Two carbon electrodes A and B are placed in the molten chlorides and an electric current is passed through the liquid as shown below: _ molten chlorides ofNand (a) What are the structural formulae of the chlorides formed by X and ¥ respectively? (b) It is found that X is a much stronger reducing agent than Y. Write half-reactions for the changes which take place at electrodes Aand B. (©) When a current of two amperes has passed through the molten, chloride mixture for two hours, calculate the mass of the product, formed at (I) electrode A (ii) electrode B. (A) @ Is ¥(s)a stronger oxidizing agent than X(s)? Gi) Is ¥*(aq) a stronger oxidizing agent than X"(aq) of the same concentration? (©) If an aqueous solution of the chloride mixture is electrolysed as shown above, what is the product formed at electrode B? (f) What do you expect to observe when a small piece of X is 190 dropped into a beaker of cold water? Write an equation for the reaction which oceurs. 31) Elements A, B and C are in the same period in the periodic table. ‘A compound X is formed by A and C, and a compound Y is formed by B and C. In the electrolysis of X and of Y, the amount of C produced from 1 mole of X is half of that produced from 1 mole of. (a) If the formula of X is represented by AC, what is the formula of Y? (b) If the ion of C has one unit negative charge, to which groups of the periodic table do elements A, B and C belong respectively? (©) From which electrode would C be liberated during the electrolysis of X? (@) Explain briefly why there is litle tendency for 4 to form an ionic compound with B. (©) Using outermost shells only, draw an electronic diagram to show how atoms of C would join together to form molecules, and name the type of bonding involved. (HKCEE) 32) Ammeter zine rod copper plate — os porous pot copper) sulphate — zine sulphate Solution solution ‘An unglazed porous pot with 1M copper(II) sulphate solution and 1 copper plate is immersed into a beaker containing 1 M zine sulphate solution and a zinc rod. A circuit is completed between the copper plate and the zinc rod, and a current can be registered by an ammeter. (@) Write ionic equations to show the reactions at the copper plate and the zine rod. 191(b) Would an electron flow occur from the copper plate to the zine rod in the external circuit? Explain your answer. (©) In what direction would the sulphate ions pass through the Porous pot? Explain your answer. (@) If the change in mass of the zinc rod at the end of the experiment is 1.00 g, what would be the change in mass of the copper plate? (©) “Magnesium is a stronger reducing agent than either zine or copper.” Explain the above statement in terms of electron transfer. What would happen when the copper plate and 1M copper(II) sulphate solution are replaced by 2 magnesium plate and 1 M ‘magnesium sulphate solution? (HKCEE) 33) sgh ammeter? 2 Thcostat 7) battery ‘The diagram above illustrates the apparatus used for the electrolysis of two solutions. Flectrode A is made of metal X, The formula of the sulphate of metal X is XSOx. Electrodes B, C and D are all made of platinum. P and Q are the poles of the battery. On completion of the circuit, metal X begins to deposit on electrode B, and gas bubbles begin to appear above electrodes C and D. (a) Which one of the poles P and Q is the positive pole? (b) Write an ionic equation for the reaction occurring at electrode A. What is this type of reaction called? (©) What would be the gases collected in the tubes above (i) electrode G, (i) electrode D? (@) After the passage of @ current of 2 amperes for 3 minutes 13, 192 34) seconds, 0.127 g of metal X is deposited on electrode B. Calculate the relative atomic mass of metal X. (1 faraday = 96 500 coulombs) The current is now reversed for 5 minutes. Describe briefly two observations that can be made at electrode B during this period. (HKCEE) battery fast core S * dioxide platinum electrodes During the electrolysis of lime water, carbon dioxide gas is bubbled continuously into the solution. The current measured by an ammeter is plotted against time, and the following graph is obtained:— Ik (@) What would be observed when carbon dioxide is bubbled continuously into the lime water? (©) With reference to the above graph, explain with the aid of ionic equations why () the current st Pis maximum, (Gi) the current decreases from P to Q, (i) the curtent at Q is minimum, (iv) the current increases from Q to R, (¥) the current shows no significant change from R to S. w signif (HKCEE) 19335) The properties of ion and tin are investigated by two experiments and the results given as follows: Result Tin filings are put into an aqueous 'No visible change solution of iron(tt) chloride, Iron filings are put into an aqueous ‘A precipitate of solution of tin(If) chloride timis produced. 1 (@) Explain the results of these experiments. Iron cans, coated with tin, are used in the canning industry as ‘tin cans’ for storing various foodstuffs. (b) Give two reasons why iron cans are coated with tin, (©) Explain what would happen if the outer surface of a ‘tin can’ is scratched exposing the iron. Give ionic equations where appropriate. HKCEE(C.D.C.) 194 1 2 VOLUMETRIC ANALYSIS TITRATIONS IN GENERAL Volumetric analysis is a method to determine the quantity or concentration of a substance by measuring the volumes of some solutions. ‘The essential process called titration consists of running a solution from 4 burette into a known volume of another solution until the two solutions have just reacted completely, ie. until the end point of the titration has been reached. ‘Volumetric analysis includes titrations of (a) acid against alkali (or carbonate) (b) oxidizing agent against reducing agent (©) one substance agains another, giving a precipitate DETECTION OF END POINT IN ACID-ALKALI (CARBONATE) TITRATIONS The following methods are often used to detect the end point of acid — alkali (carbonate) titrations: (1) By use of indicators ‘An indicator is a substance which changes colour within 2 specific pH range. Commonly used indicators are methyl orange and phenolphthalein. The pH value of a solution is a number indicating the degree of acidity or alkalinity of the solution. pH is defined as: pH = —logio(H*] where [H"] is the concentration of hydrogen ions in moles per dm? pH values usually range from 0 to 14. 195PH scale o 7 14 increasingly acidic «neutral. ——+ increasingly alkaline He?) @H>7) During an acid — alkali (carbonate) titration, there will be a marked change in pH at the end point. suitable indicator will gi perceptible colour change at the end point The following table summarizes the correct choice of indicators in different types of titrations: ‘Suitable indicator Example Titration ‘methyl orange, | HCWaq) vs. KOH(@9) phenolphtaein methyl orange | HsSO(aq) vs. NHs (a9) phenolphthalein | CH;COOH(aq) vs. NBOH(aq) one CH, COOH Eag) vs. NF Ga) methyl orange | HNO, (aa) v5. NasCOs (aq) Strong acid—srong alkalt Strong acid—weak alkali Weak acid~ strong alkali Weak acid weak alkali (2) By use of pH meter pH meter is an instrument whi oon the scale 0 to 14. gives direct reading of pH When 0.1 M hydrochloric acid is titrated against 25 cm? of 0.1 M sodium hydroxide solution, the following graph would be obtained: (ihe end point i given by the point where there is a rapid change in pH) 25 (end point) Volume of 0.1M HCI added (em?) 196 (3) By conductivity measurements ‘Changing ionic concentrations of a solution causes a change in clectrical conductivity of the solution, As acid-alkali (carbonate) titrations involve changes in concentration of hydrogen/hydroxide fons, the reactions can be followed by means of conductivity measurements. ‘Again let us consider the addition of 0.1 M HCI from a burette into a conical flask containing 25 om* of 0.1 M NaOH, The conductivity of the solution changes as shown in the following raph: Condueti 4he end point is piven by the point corresponding to the ssinimum in the graph) 2s {end pointy Volume of 0.1 M HCI added (em!) Referring to the above graph, at A Conductivity is high due to presence of large number of ‘mobile OH’ (and Na’) ions from NaOH. Ato Conductivity falls as mobile OH” are replaced by less mobile CF ions, Na'(aq) + O (aq) + H'@q) + CF@a) > Na“aq) + CI(aq) + H20(@) at E The end point. Conductivity is at a minimum when neutraliza- tion is complete. ‘The conductivity at the end point is not zero as the solution contains Na° and CI’ ions which conduct electricity (though not so good as OH” ions), FtoB Conductivity increases due to the addition of excess mobile HH (and C1’) ions from HCl. The graph is steeper than from A to Eas H" ions are more mobile than OH” ions 197(4) By thermometric titration The reaction H*(aq) + OH"(aq) —> H20(@) gives out heat. Consider 25 cm? of O.1 M NaOH placed in a polystyrene beaker together with a thermometer. 0.1 M HCI is added, a definite ‘quantity at a time, the temperature being noted after each addition. The following graph would be obtained: A to B: Temperature rises as more F to B: Temperature drops as more acid added will not liberate ‘more heat but will cool the ‘olution instead. 03 feat erste by adding : more ais : A: The end pont. Temperature E 2s (end point) Volume of 0.1M HCI added (em*) CONCENTRATION OF SOLUTION Concentration of a solution is usually expressed in either one of the following units: (1) Grams per dm? (g dm?) — number of grams of solute per dm? of ‘solution. (2) Molarity (M) — number of moles of solute per dm* of solution. Review the following relationships Molarity of _ __no. of moles of solute solution ~ Yolume of solution (in dm*) = concentration of solution in g dm? = molar mass of solute Number of moles of solute eas = molarity X volume of solution {in dm?) When the molarity of a solution is 1, it is called a molar solution, denoted as a 1 M (or M) solution. A molar solution is one which contains 1 mole of solute per dm? of solution, 198 If the concentration of a solution is known, it can be used as a standard in titration against other solutions, AA standard solution is a solution of known concentration. In the following discussion, we shall concentrate more on acid ~ alkali (carbonate) titrations, though in general, similar methods are applicable to other kinds of titrations. Example 12.1 Calculate the molarity of @ solution containing (a) 4 g of sodium hydroxide (NaOH) per dm? of solution (b) 4.9 g of sulphuric acid (HS0«) in 200 em* of solution. (a) Molar mass of NaOH = 40 4 Number of moles of NaQH = 3 = 0.1 The solution contains 0.1 mole NaH per dm? The solution is 0.1 M NaOH. (©) Molar mass of HySO, = 98 Number of moles of Hy$0s in 200 em? solution = 42. = 0,050 no. of moles of solute Volume of solution (in dm") 0.050 Molarity of solution = 025M * 00/1000 Example 12.2 Calculate the molarity with respect to sodium ions (Na') and sulphate ions (SO.*) of a 0.25 M solution of sodium sulphate. ince 1 mole of NazSO, gives 2 moles of Na’ and 1 mole of S0,* ions, molarity of Na* ions = molarity of NazSO, solution X 2 0.25 x2 = 050M molarity of SO,” ions = 0.25 MExample 12.3 (a) 2 dm> of a 5 M solution of @ substance is diluted to 25 dm’. What is the molarity of the diluted solution? (b) What volume of water must be evaporated away from 50 cm* of the dituted solution in (a) to make it 2 M? (@) On dilution, there is no change in number of moles of solute in the solution. Number of moles of the substance present = molarity X volume of solution (in dm’) = 2x5 =10 Molarity of the difuted solution no, of moles of solute 10 = © final volume of solution (in dm*) 25 oe Note: When solutions are diluted (by addition of solvent) or concentrated (by evaporation of solvent), the following relationship holds original original _ final final molarity “ volume ~ molarity * volume (the unit of volume may be om? or dm®, but must be the same throughout) (6) Since (molarity X volume)pefore evaporation = (molarity X volume) tte evaporation 04 x $0 = 2 X volume after evaporation Final volume = 2*% 59 = 19 em? 2 Volume of water that has 10 be evaporated away from the solution = 50 — 10 = 40 em? Example 12.4 Concentrated hydrochloric acid has a relative density of 1.2 and contains 32% by mass of hydrogen chloride, Calculate the volume of this liquid which would be required 10 prepare 250 em’ of 0.80 M hydrochloric acid. 200 To make 250 cm* of 0.80 M HCI solution. number of moles of HCI required = molarity X volume (in dm‘) + 030 22 = 029 O20 65 754 13% = 28 Since it has a relative density of 1.2, ie. a density of 1.2 g em®, volume of concentrated hydrochloric acid required mass | 23° CALCULATIONS IN TITRATION In dealing with problems in titration, we should always write down balanced equation for the reaction. This gives the ratio in moles of the reactants and products, For the reaction between two solutions of A and B, aA +bB > eC + dD no. of moles of A _ a no. of moles of Bb MaVa or BOM AV a) = a ava (MaVa) = a(Me Va) where My = molarity of A; Vy = volume of A (in dm*) Mg = molarity of B; Vg = volume of B (in dm?) Note: If V4 and Vg are both expressed in em? the above relationship still holds. In general, there are two ways of performing a titration: (a) Direct titration; Just the right amount of titrant (the solution in the burette) is added to the solution in the conical flask. (See Example 12.5) (b) Back titration: Excess amount of a standard solution is first added fo the solution (of unknown concentration) in conical flask. The amount of substance in excess is then determined by titration against another standard solution. (See Example 12.7) 201Applications of volumetric analysis, In elementary chemistry, volumetric analysis is often employed to determine: (1) concentration of a solution (standardization) (see Example 12.5) (2) charge of an ion (see Example 12.6) (3) percentage purity of a carbonate or hydrogen carbonate (ee Example 12.7) (4) percentage of ammonia in an ammonium salt (or percentage purity of an ammonium salt) (cee Example 12.8) (5)*basicity of an acid (see Example 12.9) (©) molar mass of a substance (Gee Example 12.10) (7) atomic mass of metal (Gee Example 12.11) (8) number of molecules of water of crystallization of a hydrate (Gee Example 12.12) (©) composition of a mixture (see Example 12.13) Example 12.5 2.65 g of sodium carbonate (NayCOs) were dissolved in water and ‘made up to 250 cm? solution. 25.0 cm? of this required 20,0 cm? of a hydrochloric acid solution for complete reaction, Find the molarity of the hydrochloric acid. Molarity of the Na,COs solution From equation, 2HCI(aq) + Naz CO3(aq)—> 2NaCl(ag) + H O(8) + COs(g) MuyciVuc. = 2MNa,CO; Vico, Muct X 20.0= 2 X 0.100 X 25.0 Molarity of HCL = Mycy = 0.250 M * basicity of an acid is the number of moles of hydrogen ions which can be produced from one mole of the aid 202 so lorie way of ing his rem i Misr mas of NCO, = 106g Number fms of $0, in 280 cn of ton = 2S = 0.0250 Number of moles of Na,CO, in 25.0 cm? of solution = oomso 2HCI(aq) + NazCO3(aq) —> 2NaCI(aq) + Hs O(®) + CO3 (8) From the equation, 2 moles of HCl react with 1 mole of NazCOs, number of moles of HCI in 20.0 em? of solution = 0.00250 x 2 = 0.00500 0.00500 x 4000 0.250 oe Number of moles of HC! in 1000 em? of solution Molarity of the HCl solution = 0.250 M Example 12.6 5 cm? of a 0.05 M solution of a metallic chloride was added 10 various volumes of 0.1 M solution of silver nitrate, The mass of silver chloride precipitated was plotted against the volume of silver nitrate solution added. ‘Mass of slver chloride Volume of siver nitrate solution (em*) (a) Give the ionic equation for the precipitation reaction. (b) What volume of 0.1 M silver nitrate solution is required to precipitate all the chloride ions? 203(c) How many moles of chloride ions are there in 5 cm* of the 0.05 M metallic chloride solution? (a) How many moles of chloride ions are there in one mole of the metallic chloride solution? (e) What is the number of charges on the metallic ion? (HKCEE) (a) Ag‘(eq) + CT(@q) —> ABCs) (b) From graph, 7.5 cm’ of 0.1 M AgNO; solution are required to precipitate all the chloride ions. (©) Number of moles of CI ions = number of moles of Ag* ions required to precipitate all CI ions 15 = OLX Thag = 75K (@) Number of moles of metallic chloride in 5 cm* of 0.05 M metallic i Soe 4 chloride solution = 0.05 X ap = 2.5 X 10 So 2.5 X 10% mole of metallic chloride contains 7.5 X 10 mole of CI ions. Number of moles of CI ions in one mole of the metalic chloride 18X10" solution = 337 its = 3 (©) 3 positive charges. Example 12.7 50.0 em® of 0.500 M nitric acid were added to 1.28 g of a sample of calcium carbonate containing sand as impurity. The excess acid was found to be neutralized by 20.0 m° of 0.400 M sodium hydroxide solution. Find the percentage purity of the calcium carbonate. Number of moles of NaOH used to neutralize excess HNO 200 _ 9 = 0.400 x sp5 = 0.00800 According to the equation HNOs(aq) + NaOH(aq) —> NaNOs (aq) + H20(@) number of moles of excess HNO, = 0.00800 204 Number of moles of HNO, originally added = ae iainlly added = 0.500 x 508 = 0.0250 Number of moles of HINO3 which reacted with CaCO = 0.0250 — 0.00800 0.0170 From the ecuation 2HNO) (ag) + CACOs (6) —> Ca(NOs)s(aq) + CO3(g) + HOC) number of roles of CaCO, in the sample = 00170 x! = osesea Molar mass of CaCO, = 100g Mass of CaCO, in the sample = 0.00850 X 100 = 0.850 ¢ Pact purty af the ample of cad, = 2822 x 109% = 66.4% Example 12.8 2.15 g of an ammonium salt were boiled with 50.0 cm of 1.00 M sodium hydroxide solution until all ammonia was expelled. The excess alkali required 25.5 cm* of 0.400 M hydrochloric acid for neutralization, Calculate the percentage by mass of ammonia in the salt. Number of moles of HCI required to neutralize excess NaOH. 5 BS 0.400 x FF = 0.0102 From the equation HOI(aq) + NaOH(aq) — Nacifag) + H50(2) ‘number of moles of excess NaOH = 0.0102 Number of mies oF WOH aed at str = 100 $28 « gop Number of moles of NaOH that reacted with ammonium salt 0.0500 — ¢.0102 = 0.0398 From the equation NH,'(aq) + OH'(aq) —> NH3(@) + H,.0(8) number of moles of NH; expelled = 0.0398 205Molar mass of NHy = 17 g Mass of NH, expelled = 0.0398 X 17 = 0.677 g recep by nas of yn te sit = 2677 x 1006 = 315% Example 12.9 10.8 g of an acid (molar mass = 98 g) were dissolved in water and the solution made up to 250 cm?. 25.0 em® portions of the acid solution were titrated against 1.50 M potassium hydroxide solution, using a suitable indicator, until the solution was completely neutralized. The titration results are tabulated below: Titration number Volume 1 2 3 4 of 150M KOH(aq) inal burete m2 | 43 | 228 | 457 reading (crm* ) cere 13 | 242 18 | 238 reading (cm* ) (a) Name an apparatus suitable for making up the acid solution to 250 cm. (b) Name an apparatus suitable for the withdrawal of 25.0 cm? portions of the acid solution, fe) Calculate a reasonable average for the volume of 1.50 M potassium hydroxide solution required to neutralize 25.0 cm of the acid solution, (d) Determine the basicity of the acid. (@) Volumetric flask (the 250 cm? type). (b) Pipette (the 25.0 cm? type). (©) The volumes of 1.50 M KOH delivered in titrations 12,34 are 22.9 em*, 22.1 cm®, 22.0 cm? and 21.9 cm? respectively. The value 206 22.9 cm? deviates a lot from all the others and may be discarded. Hence 2 reasonable average volume 22 + 22.0 + 21.9 3 = 22.0 em? (@) No. of moles of KOH required to neutralize 25.0 cm* of the excess wn 220 wid = 150x 22 «003s oof mata in 20am? statin = 198. 0.1 No. of mole of acid in 25,0 em? solution = 0.11 x 252 = 0.011 Let Hyd be the formula of the acid, where n is the number of ionizable hydrogen atoms Then equation for the neutralization is H,A(aq) + nKOH(aq) —> KnA(aq) + nH,0(8) No. of moles of KOH 0.033 _ an No. of moles of HA 1) O01 ~ 1 ~ne3 ‘Thus basicity of the acid is 3, ic. the acid is tribasic. Example 12.10 1.44 g of a dibasic acid (H,X) were dissolved in water to make up 10 250 cm solution. 25.0 cm® of this required 32.0 cm® of 0.100 M sodlum hydroxide solution for complete neutralization, Find the molar mass of the acid no Number of moles of NaOH in. cm? of solution = — er fol of OM in 32.0 eno lation = 100x322 Sem From eatin of ecto 1H, X(aq) + 2NaOH(aq) —> Na, X(aq) + 2H, O(8) number of moles of H2X in 25.0 cm? of solution = 0.00320 X oontea Number of mls of Xn 250 on of solaton = corso x 282 = corso 27Hence 0.0160 mole of H,X has a mass of 1.44 g. Lag Sores ~ 9°08 Molar mass of HX = Example 12.11 0.720 g of a metal X dissolved completely in 50.0 cm* of 1.00 M sulphuric acid, which was then found t0 require 80.0 cm? of 0.500 M sodium hydroxide solution for complete neutralization. If the oxidation state of the metal in the salt is +11, what is its atomic mass? Number of moles of NaOH required to neutralize the excess H,SO, - 80.0 _ = 0500 x 7Boy = 0.0400 From the equation H,S04(aq) + 2NaOH(aq) —* Naz SO, (aq) + 2H30(@) umber of moles of exces 180 = 0.0400 x = 00200 4 50.0 Number of moles of HaSO, added at start = 1.00 x 7555 = 0.0500 Number of moles of H,$O, that reacted with metal X (0.0500 - 0.0200 = 0.0300 From the equation X(8) + HzSO4 (aq) —* XSO4(aq) + Ha(g) number of moles of X used = 0.0300 0720 __ = 0.0300; No. of moles of X= SE ye > Atomic mass of X = 24.0 Example 12.12 4.0 of a sample of hydrated sodium carbonate, of formula NazCO3.nbl0, are dissolved in water and the solution made up to 250 cm. Using methyl orange as indicator, 25 cm? of this solution require 29 cm? of 0.05 M sulphuric acid for neutralization. Caleulate n, the number of molecules of water of crystallization, in the sample of sodium carbonate. (HKCEE) 208 Molar mass of NayCOy.nlz0 = (23X 2+ 12+16X 3+ 18n) = (106 + 18n) g ‘Number of moles of NayCOs.nlH,0 in 250 cm? of solution _ 40 T06 + 180 Number of moles of NagCO3.nH0 in 25 cm? of solution 4025 40 106 + 18n * 250 ~ 106+ Téa * 10 According to the equation [NaC03-nH;O(aq) + Hy$0«(aq) —+ NaySO«(aq) + COa(g) + (0 + 1) H,0(@) number of moles of NagCO3.al¥,O0 in 25 em? of solution = number of moles of HySOs in 29 cm? of 0.05 M H2S0, 29 0.05 x ;2%, = o0014s do yt = de s Tos + 180 * 10 ee no Note: 1 should be a whole number. The calculated value n = 9.4 indicates that the compound is NazCO3.10Hz0, probably con- taminated with a little Na;CO,.9H20 and/or NazCOs.H;0. Example 12.13 1.46 g of @ mixture of sodium hydroxide and anhydrous sodium carbonate were dissolved in 100 cm? of water. This solution required 30,0 cm? of 1.00 M hydrochloric acid for complete reaction. Find the percentage composition by mass of the micture, Let x g be the mass of NaOH, then mass of NazCO; = (1.46 — x)g NaOH(aq) + HCl(aq) —+ NaCi(aq) + H,0(2) 209'NagCOs(aq) + 2HCI(aq) —> 2NaCi(aq) + CO2(g) + H,0(2) 146 - x 106 mole %) mole From the equations, total amount of HCI required = [Xp 246 =) oy 40 106 Mes 228 66300 me and from the gen dt, this amount is 100 x 222 = 9.0300 mek x, 2046—x) _ Bo 2046=9 - ono Solving the equation, we ge x = 0.400 Percentage by mas of OH = 2422 x 109% = 2748 percentage by mass of NazCO3 = 100% —27.4% = 72.6% Note: The volume of water (100 cm*) used to dissolve the mixture does not enter into calculation in this example EXERCISE 12 1) Calculate the mass of solute in each of the given solutions: (@) 500 em? of 0.1 M NaOH (©) 200 cm? of 0.200 M Na3COy (©) 100 em? of 1.0 M HsS0, (a) 400 cm? of 0.500 M NH,Cl (©) 300 em* of 0.200 M H,C20, 2) What volume of hydrogen chloride, measured at s.t.p. is required to make 100 em? of 0.25 M hydrochloric acid? 3) (@) What volume of water must be added to 25 cm’ of 1.0 M sodium hydroxide solution to make it 0.20 M? (b) What volume of water has to be evaporated away from SO cm of 0.10 M sodium chloride solution in order to concentrate it to 0.25 M? 210 4) Concentrated sulphuric acid of density 1.84 g cm” contains 98% by mass of sulphuric acid. What volume of the concentrated acid should be diluted to prepare 250 cm? of 0.10 M solution? 5) What volume of 0.050 M sulphuric acid will be required for complete reaction with each of the following solutions? (a) 25 em? of 0.10 M NaOH (©) 50 em? of 0.20 M KOH (©) 100 em? of 0.10 M Na,CO3 (@) 100 cm? of 0.10 M NazCOs. 10H;0 6) (a) An acid reacts with an alkali according to the equation (aq) + OF" (aq) — H0@) ‘A 0.50 M solution of a monobasic acid was titrated against an alkali solution, using a suitable indicator. 25 em of the alkali solution required 20 cm? of the acid for neutralization Calculate (i) the molarity of the alkali solution with respect to OH ions (ii) the mass of OH’ ions per dm? of solution (b) 25 cm? of the alkali solution mentioned in (2) required 10 om? ‘of oxalic acid (H,C,0,) for neutralization, phenolphthalein being used as indicator. Find the molarity of the oxalic acid. (Hint: Oxalic acid is a dibasic acid.) 7) On diluting a sample of ethanoic acid (CH, COOH) five times, it was found that 25 cm* of the diluted solution required 30 cm? of 0.10 M sodium hydroxide solution for complete neutralization. What was the concentration of the original ethanoic acid in (a) mol dm (b) g dm*? 8) What volume of ammonia, measured at s.tp., is required to neutralize 100 cm? of 0.500 M'sulphuric acid? 9) 8.0 g of magnesium are treated with 100 cm’ of dilute sulphuric acid containing 196 g of acid per dm°. Calculate (a) the mass of ‘magnesium left (6) the volume of hydrogen produced at room conditions. 10) 25 cm? ofa solution of sodium hydroxide were placed in a polystyrene cup, together with 2 thermometer. The temperature was noted and 0.50 M hydrochloric acid was added, 5 em? at a time, the temperature beeing noted after each addition, ‘The temperature readings were auplotted against ‘volume of acid added’, and the following graph (b) Write the ionic equation for the neutralization, was obtained. (©) What is the volume of 2 M NaOH solution required to neutralize 20.0 em? of the HCI solution? (@) What is the molarity of the HC! solution? (©) Explain the drop in temperature from B to C. (In another experiment 0.5 M NaOH solution is used instead of 2 M NaOH solution to neutralize 20.0 em? of the same HCl solution. Explain whether there would be any difference in the amount of heat produced by this neutralization compared to “Temperature CC) that using 2 M NaOH solution, HKCEE (C.DC_) oi 2% 30 40 $0 ‘Volume of aeid added (cm*) 12) i xem? of the 51.0¢m? of the tom acid have been acid have been Refer to the graph and answer the following questions: #50. ‘added added (@) Why was the experiment carried out in a polystyrene cup? (©) By drawing two straight lines through the points, find the volume of acid required to neutralize 25 cm? of the alkali solution, (c) What was the molarity of the alkali solution? (a) What was the molarity of the solution with respect to Na’ ions | when 50 cm? of acid had been added to 25 em? of the alkali | solution? | . ¢ 11) 2M NAOH solution is added continuously to 20.0 cm? of a HCI . solution in an insulated calorimeter. The temperature of the mixture | ritammeer yes milange hes ilar Bes is plotted against the volume of NaOH solution added, as shown in oe ae the graph below. | AA circuit is set up as shown in figure A. The beaker contains 100 em* of 0.50 M barium hydroxide solution and a few drops of methyl orange. ‘The milliammeter gives a high reading when two electrodes P and Q ate placed in the solution. 1.0 M sulphuric acid is then © added to the solution from a burette as shown. The milliammeter ives a low reading (nearly zero) and then a fairly high reading in figures B and C respectively (@) What are the colours of the indicator in figures A and C? eee (b) Would you observe any precipitate in the beaker in figure B? Volume of NaOH solution (em*) Explain ‘Temperature (©) Why does the milliammeter give a low reading (nearly zero) (@) Explain the temperature change from A to B on the graph. in figure Banda fairly high reading in figure C? 213,(@) Calculate the volume of the acid required to make the milliammeter reading lowest (nearly 7270). (©) Can phenolphthalein be used as indicator instead of methyl ‘orange in the titration? Explain (6) What type of reaction occurs at electrode (i) P (i) Q? (@) Write halfequations for the half-reactions at the two electrodes in case of figure C. 13) (a) Hydrogen peroxide solution decomposes as follows 2H,0, (aq) —+ 2120) + 0216) 100 cm? of @ hydrogen peroxide solution are decomposed catalytically to give 480 om* of oxygen at room temperature and pressure Assuming that complete decomposition has taken place, caleulate the molarity of the hydrogen peroxide solution. (©) Acidified potassium permanganate solution oxidizes oxalic (ethanedioic) acid to carbon dioxide and water. 2Mn04{(aq) + SH;C20x(aq) + 6H'(2q) —+ 2Ma*(aq) + 10CO, (4) + 81302) 25 cm’ of 0.20 M oxalic acid solution required 20 em? of acidified potassium permanganate solution for complete reaction. Find the molarity of the potassium permanganate solution 14) 2.44 g of barium chloride crystals (BaCl,.2H;0) were dissolved in water, To the solution was added 100 cm? of 0.125 M potassium carbonate (K3CO5) solution. The precipitate formed was filtered, washed and dried. Calculate (a) the mass of barium carbonate (BaCOs ) formed (b) the volume of 0.10 M nitric acid required to react completely with the excess potassium carbonate in the filtrate, 15) 25.0 cm® of a 0.10 M solution of barium hydroxide were placed in a conical flask fitted with electrodes. The electrical conductivity of the solution was measured. Sulphuric acid was then added, 5.0 cm? at a time, the conductivity being measured after each dition, A precipitate was formed during the titration, the reaction being represented by the equation Ba(OH), (aq) + HySO4(aq) —> BaSOq(s) + 2H, 0(&) 24 A graph of the results is shown below: lectscal conductivity a a Volume of acid added (em?) (@) Account for the shape of the graph, including the decrease of conductivity almost to zero at one point and then the steep ris. (b) What is the volume of acid required to reach the end point of the titration? (©) What is the molarity of the sulphuric acid solution? 16) 25 cm? of a calcium chloride solution are added to SO cm? of a 0.2 M sodium carbonate solution. The precipitate formed is filtered, washed and dried. The excess sodium carbonate in the filtrate requires 26.5 cm? of 0.1 M hydrochloric avid for complete reaction (Ge. until no mote carbon dioxide is formed). (a) Write equations for the reactions, (b) Assuming precipitation is complete, what is the mass of the precipitate formed? (©) Calculate the molarity of the calcium chloride solution. (HKCEE) 17) (@ Solution X contains 20 g of sodium hydroxide per 250 em* of solution. Calculate the molarity of the solution, (©) Solution ¥ contains 18 g of a solid acid (HA) per 100 em* of solution. The molecular mass of the acid is 90. Calculate the molarity of the solution. (©) 50 cm? of solution X ate found to react completely with 25 em* of solution ¥. ys18) 19) 20) 21) 216 () Calculate the number of moles of sodium hydroxide in 50 em* of solution X. Gi) Calculate the number of moles of Hyd in 25 cm? of solution ¥. (ii) How many moles of sodium hydroxide react with 1 mole of Hyd? (iv) What is the value of n in Hy? (8) Write an equation for the reaction which takes place between solutions X and ¥, 1.00 g of calcium carbonate was dissolved in 40.0 em® of a hydro chlotic acid solution. The excess acid required 25.0 em? of a certain sodium hydroxide solution for neutralization. 20.0 cm? of this sodium hydroxide solution neutralized 16.8 cm? fof the original acid, Calculate the molarties of the hydrochloric acid and sodium hydroxide solution. ¥ is a solution of a solid base XOH. 10 cm? of Y are added to 100 cm? of a 0.1 M solution of sulphuric acid and the mixture requires 12.5 cm? of a 0.4 M sodium hydroxide solution for complete neutralization. What volume of Y is required to make 1 dm? of 0.1 M solution of XOH? (HKCEE) (@) 5.00 g of an impure sample of potassium carbonate (KxCOs) required 34.2 cm’ of 2.00 M hydrochloric acid for complete reaction. What is the percentage purity of the carbonate? (Assume that the impurities in the sample do not react with hydrochloric acid.) (b) 2.00 g of marble were added to 80.0 em? of 1.20M hydrochlor acid. The unreacted acid was exactly neutralized by 28.8 cm of 2.00 M sodium hydroxide solution. Calculate the percentage of calcium carbonate in the marble. (@)- A sample of concentrated sulphuric acid has a relative density of 1.85 and contains 91.77% by mass of sulphuric acid. Calculate (@ the molarity of the concentrated sulphutic acid sample Gi) the volume of this acid sample required to prepare 1 dm* of 0.05 M sulphuric acid. (b) 0.52 g of a sample of magnesium oxide containing impurities which do not react with acid, was heated with 40 cm? of 0.645 M sulphuric acid. The excess acid required 27.16 em? of 0.98 M sodium hydroxide solution for complete neutralization, Calculate () the volume of 0.645 M sulphuric acid required to react with the sample of magnesium oxide i) the percentage by mass of pure magnesium oxide in the original sample, (HKCEE) 22) An experiment to find the percentage by inass of ammonium sulphate in a sample of this compound (contaminated with sodium sulphate) was carried out as follows: 1.65 g of the sample were made up to 250 cm? of solution. 25.0 em? of this were boiled with 25.0 em" of 0.200 M sodium hydroxide solution until all the ammonia had been expelled from the salt, The remaining liquid required 25.4 cm? of 0.100 M hydrochloric acid for neutralization, (@) Write an equation for the reaction between hydrochloric acid and sodium hydroxide solution. (b) How many moles of hydrochloric acid were present in 25.4 cm? of 0.100 M solution? (©) How many moles of sodium hydroxide were neutralized by the hydrochloric acid? (@) How many moles of sodium hydroxide were present in 25.0 em? of the original 0.200 M solution? (©) From your answers in (c) and (4), how many moles of sodium hydroxide must have reacted with ammonium sulphate to expel (©) Write an equation for the reaction between ammonium sulphate and sodium hydroxide solution, (@) How many moles of ammonium sulphate were present in the original sample (je. in 250 cm? of the original solution)? (®) What mass of ammonium sulphate is this? (@) Calculate the percentage by mass of ammonium sulphate in the original sample. 23) 25.0 cm? of a 1.0 M solution of sodium hydroxide were placed in a flask, 1.40 g of an impure specimen of ammonium, chloride was added. The flask and its contents were then carefully heated until no more ammonia gas was evolved. The resulting solution was found to be alkaline and was diluted to exactly 250 em’. SO cm? 217of this solution required 5.10 em? of 0.1 M hydrochloric acid for neutralization, Calculate the percentage purity of the original impure ammonium chloride. (HKCEE) 24 5.00 g of a sample of an ammonium salt (NH,X) were boiled with excess sodium hydroxide solution and the evolved ammonia was absorbed in 120 cm? of 0.500 M sulphuric acid. The remaining solution (Containing excess acid) was made up to 250 cm? with water, and 25.0 cm® of the resulting solution required 264 cm? of 0.100 M sodium hydroxide solution for neutralization. Calculate the percentage by mass of ammonia in the sample of NHX. 25) 25.0 cm? of 0.120 M sodium hydroxide solution were neutralized by 30.0 cm? of a solution of a dibasic acid (HX) containing 6.30 g of the acid per dm’ of solution. Calculate (a) the molarity Of the acid solution (b) the molar mass of the acid. 26) 1.5 g of a dibasic acid containing two molecules of water of crystallization are dissolved in distilled water and the solution made up to 250 cm?. 25 em? of this solution require for neutralization 26.2 em* of decimolar sodium hydroxide solution. Calculate (a) the relative molecular mass of the crystalline solid acid (b) the con- centration of the anhydrous acid in grams per dm? (AKCEE) (Hint: Decimolar means 0.1 M) 27) A solution of acid X containing 48.5 g of X per dm? was prepared. 25.00 cm? of this solution exactly neutralized 31.25 cm? of a solution of sodium carbonate, the concentration of which was 21.2 g of NazCO3 per dm?. Calculate (@) the volume of acid which reacts completely with 1 dm? of the carbonate solution (b) the mass of X Which reacts completely with 106 g of sodium carbonate. If the formula of X is H3NSOs, deduce (c) the number of moles ‘of the acid which reacts completely with one mole of sodium carbonate (@) an equation for the reaction 28) A water soluble compound, MHCOs, reacts with hydrochlorie acid according to the equation ‘MICO, (aq) + Haq) —> MCI(aq) + CO;(@) + H,0(®) It was found that 25.0 cm? of a solution containing 10.8 g dm”? of MHCOs reacted with 27.0 cm? of hydrochloric acid solution of concentration 3.65 g dm”. Calculate 28 (a) the molarity of the hydrochloric acid (b) the molarity of the MHCO; solution (©) the molar mass of MHCO3 (4) the atomic mass of M. 29) The number of molecules of water of crystallization, n, in hydrated barium chloride, BaCl,.nH,0, can be found from the following experiment. 3.00 g of hydrated barium chloride were dissolved in water and ‘made up to 250 cm? of solution. 25.0 em® of this solution were boiled with 12.5 cm? of 0.200 M sodium carbonate solution (an excess) and, after cooling, the white precipitate was filtered off. ‘The filtrate required 12.7 em? of 0.200 M hydrochloric acid for complete reaction. (@) What was the white precipitate formed? (b) What did the filtrate contain? (©) Write an equation for the reaction which took place when hydrochloric acid was added to the filtrate. (@ How many moles of HCI were present in 12.7 em? of the 0.200 M hydrochloric acid? (©) How many moles of sodium carbonate must have been present in the filtrate? (©) How many moles of sodium carbonate were present in 12.5 em? of the original 0.200 M solution? (@) Hence calculate number of moles of sodium carbonate that reacted with the barium chloride. (h) Write an equation for the reaction between barium chloride solution and sodium carbonate solution. (How many moles of barium chloride were present in 25.0 cm? Of the solution used? (What mass of the hydrated salt BaCl, .nF, 0 is this? (&) Calculate the molar mass of BaCi, .nH; 0. (@) Hence find the value of n. 30) 8.0 g of a sample of hydrated sodium carbonate, Na;COs.nll;0, are dissolved in water and the solution is made up to 250 cm? . Using methyl orange as indicator, 25 cm?® of this solution require 28 cm* of 0.10 M sulphuric acid’ for complete reaction. Calculate n, the 219number of molecules of water of crystallization, in the sample of sodium carbonate erystas. 31) 1.26 g of a hydrated dibasic organic acid of anhydrous molecular mass 90 were made up to 250 cm? with water. 25.0 cm? of this solution required 20.0 cm? of 0.100 M potassium hydroxide solution for neutralization. Calculate the number of molecules of water of crystallization per molecule of the hydrated acid 32) Sodium hydroxide solution is added in excess to 2.0 g of a mixture of ammonium sulphate and sodium sulphate. On heating, the ammonia liberated is dissolved in 25 cm? of 0.5 M sulphuric acid, ‘The excess acid required 27.0 cm? of 0.1 M sodium hydroxide for complete neutralization. (@) Write chemical equations of the reactions. (b) Calculate the percentage composition of the mixture. (HKCEE) 33) 3.60 g of a solid mixture of sodium carbonate-lO-water (Na;COs.10H,0) and sodium hydrogen carbonate (NaHCOs) required 23.0 em? of 150 M hydrochloric acid for complete reaction, Calculate the percentage by mass of each substance in the mixture, 34) A powder mixture of sodium hydroxide and anhydrous sodium ‘carbonate required 75.0 em? of 0.200 M sulphuric acid for complete reaction. The volume of carbon dioxide evolved (corrected to s.t-p.) was 112 om*. Calculate the composition by mass of the original mixture 35) 100 em? of a solution B containing nitric acid and hydrochlovic acid required 68.0 em? of 1.00 M sodium hydroxide solution for exact neutralization. 500 cm? of B reacted with excess silver nitrate solution to give 2.725 g of silver chloride precipitate. Find the concentration (in g dn) ofeach acid in B. 36) Potassium permanganate solution oxidizes iron(II) salt to iron({tl) salt according to the following ionic equation: SFe*(aq) + MnO, (aq) + 81"(aq) —> SFe™(aq) + Mn?"(aq) + 4H,.0(%) 1817 g of potassium permanganate are dissolved in water to give 250.0 cm? of aqueous solution. 2.185 g of an iron(Il) salt are 220 dissolved in water and the solution made up to 100 em?. 40,00 cm? of this iron({f) salt solution require 25.00 em? of the permanganate solution for complete reaction, (@) What is the molarity of the potassium permanganate solution? (b) What is the molarity of the Fe ions in the iron(II) salt solution? (©) Given that 1 mole of the iron(II) salt contains 1 mole of Fe" ions, what is the molar mass of the iron( tl) salt? (@ What is the percentage by mass of iron in the salt? 211 PERIODICITY & 3 GROUP TRENDS PERIODIC TABLE AND PERIODICITY You have leamt in Chapter 2 that when elements are arranged in horizontal rows in increasing order of atomic number, a Periodic Table of elements can be built up (se p. 453). It is interesting to note that elements having similar atomic, physical and chemical properties recur at regular intervals inthe table PERIODICITY is the recurrence of similar phenomena at regular internals. PERIODICITY OF SOME ATOMIC PROPERTIES Electronic configuration For an element in the main groups, the following rules apply: (1) Number of occupied electron shells of the element = period number (2) Number of electrons in the outermost shell = group number (Wote: Group 0 elements (except helium) have 8 electrons in the ‘outermost shell; helium has 2.) Example 13.1 To which period and group of the Periodic Table does each of the following elements belong? In each case, state whether the element is a ‘metal or non-metal. Element Electronie configuration w 2, 8, 18, 18,7 = 2.88 Yy 2,8,81 Zz 2,8, 18, 32, 18,5 22 W belongs to Period 5, Group VII; it is a non-metal X belongs to Period 3, Group 0; tis a non-metal. Y belongs to Period 4, Group I; it isa metal Z belongs to Period 6, Group V;it is a non-metal Atomic size On moving across a period, there is @ gradual decrease in atomic size in main group elements (from Group I to Group VII). This is because of increasing nuclear charge which pulls electrons closer. (Wore: In passing down a group, there is @ gradual increase in atomic size as the number of electron shells increases.) Gow 1 om om WV Movi F smallest atomic size Decreasing largest cs Example 13.2 By referring to the Periodic Table at the end of this book, judge which atom has the largest size in each of the following cases: (a) Li,Na,K (6) CL, BrT (c) Na, Mg, 8, Cl (d) Pb, P.O (e} Si, Se, Br @) K (e) 1 (©) Na (@) Pb (e) It cannot be predicted just from their positions in the Periodic Table. 23Electronegativity {In going across period, electronegativity value increases. (Wore: In passing down a group, electronegativity value decreases.) Group | iM om Ww ovo vovIt F ‘most electronegative clement Increasing lectronegativity feast lectroncgetive element cs (most electropositive element) PERIODICITY OF SOME PHYSICAL PROPERTIES In the following discussion, we shall confine our study to the first twenty elements of the Periodic Table. Melting point ‘A graph of melting point against atomic number is shown on next page. Across a period, melting point increases from Group I to Group IV, then decreases sharply to low values in Groups V to 0. Elements in Group 1 to Ill have *giant metallic structures, Their atoms are bound together by strong metallic bonds most of which are not broken when the metal melts, Hence their melting points may not be high. To a first approximation, the strength of metallic bond depends upon the number of outer shell electrons, and thus increases from Group | to III. So a corresponding increase in melting point is observed. For Group IV elements (C and Si), there is interlinking of a large number of atoms to form a giant covalent structure. Since nearly all the strong covalent bonds have to be broken before melting can occur, @ high temperature is required, corresponding to a maximum in the graph. * Anexception is boron which sa semimetal(metallod) with gant covalent structure. 224 For Group V to 0, the elements in solid state have simple molecular structures in which molecules are attracted by relatively weak inter- molecular forces (van der Waals’ forces). In melting the solid, only these ‘weak forces (and not strong covalent bonds) need to be overcome. So their melting points ae low. 4000} (diamond) Temperature CC) 3 2000} Oar Ba 7k e (Ghombie) 6% ‘Atomic number Boiling point ‘The variation of boiling point with atomic number has similar patterns as that for melting point. It should be noted that boiling points of metals are much higher than ‘their melting points. This is because in boiling a metal, the metalic bonds present in the liquid have to be completely broken ‘The boiling points of giant covalent structures (such as C and Si) are very high, but not much higher than their melting points. This is because nearly all of the covalent bonds have been broken in melting. Atomic volume ‘Atomic volume of an element is the volume occupied by the amount of the element that contains one mole (6.02 X 10%) of atoms (at a given ‘temperature and pressure), 225[Atomic volume (in em?) = 2389f1 mole of atoms (ng) density (in gem™*) eee . ai of Note that in cases of elements which are gaseous at room temperature 5753| 60/3282 S38 ‘nd pressure, their densities as liquids at their boiling points are taken gige|oc|e82 5 CHE The following graph shows vatiation of atomic volume (at room ot By || é . ‘temperature and pressure) with atomic number. aps 828 ey) & |#lge, $9 fifi lsgiees2|4|4) 2 | sjgezle En arse 1°38" s 18) 2 Belial eile Bo s]2| 2 [2 3 i fe) tae le eee 3 i eae 2 ial? Se 5 e./ alg 22f| 2 a £483| 35 5 | |o2]2 i £434 \ée i 2H 2 gee lee 5B aS ss as) a] f al¢ fe . + io 5 20 22/8 fg| ¢ z ‘Atomic number as g*| F 5 It can be seen from the graph that atomic volume falls to the centre ; 4 22 re cof each period and then rss again is |e] 2 |, 32 [8 a8 = 2 S #3 |e VARIATION IN CHEMICAL PROPERTIES ACROSS 4 z=) 2 2 5 PERIOD 3 z g Patterns in properties of the elements £ : i 3 | $] i. s| ¢ 2.8 Grow umber [1 [u [m]w [v [v [vu | o | le Ela| © |i) gee 3 Hlement mm [we [a fs fp fs [a [ar ee leetaa es 4 =| ess ed £12 3 5, 713 ere 2,8,1| 2,8,2| 2,8,3] 28,8 s 1 i i contgwasion _ [281] 282] 20 3 sl. . gle eli oo = a] 42 /¢ 3 3/283] = exitetom member |“ |*2 [23 | fem Leaf! |? E12 |? ; ety 4 Tam | simple molecu state 3 L — sant metic g =| : structure Grructur Pe | Se | Cn | Ar S a [2], [38 g |e hea ‘i reer A a/ Be 2] /He| 2 E edo sna, peak RA‘andior — sone A BS |e) [essa] 5 Redor strong "RA. [ue Poa [anor EL ELE) ge [3/2] 2 |Z = eo el gata sce ale = R.A. stands for reducing agent; O.A. stand for oxidizing agent. 6 227GROUP TRENDS Elements of the same group have similar properties because of the same number of outer shell electrons. Besides, they may also have properties in which there is a gradual change with increasing atomic number. ‘The tendency with which a certain property changes within a group is called group trend. In the following account, we shall look at some group trends in Groups I and VII. reenishyellow = Gh reacts with Chiorine ae covalent water to give acids ‘Sulphur dichloride ‘Sch, red tiquia Group 1: the alkali metals Atomic number | Element | Symbol | Electronic configuration . 3 Lithium | Li 21 n Sodium | Na 281 19 Potassium | K 2881 37 Rubidium | Rb 28.18.81 55 Caesium | Cs 2,8,18,188, All have only one outer shell electron; a stable MM" ion (with the same electronic onfiguration of the preceding noble gas) is formed easily by losing this valence electron. non-conductors | Phosphorusam) tetrachloride | chloride Pols olourless liquid simple molecular structure. ——_______,. predominantly covalent Silicon Side Similarities and group trends (1) They are ail motals of low density. The atoms ate held together by metallic bording. (2) As only one valence electron is available, the metallic bonding is weak and hence they are solids of low melting points and boiling points which decresse steadily down the group. . (3) Being strong reducing agents, they are all highly reactive. For example, t they all react with water to form aqueous alkali and hydrogen gas (4) On descending the group, the reactivity of the elements increases. This is because here the reactivity depends on the ease with which the metal atoms lose electrons. That is, = MoM te ‘This process becomes easier as the group is descended (large atom loses electrons more easily). Thus reducing power (reactivity) increases in the order Li(s) < Na(s) < K(s) < Rb(s) < Cs(s) al hydrolysed; chloride reacts with water, giving HCI fumes ‘Aluminium chloride partly Tonle, partly ovalent ant Gonie= tovalent) lattice poor AlCl, ‘white rolid Magnesiom chloride Mach, ‘white crystalline predominantly fonie Title or no hydrolysis volid “lid dissolves readily bydreysis Sodium ehloride Ne Patterns in properties of the chlorides Colour and state fat 25°C) Chemical bonding conductivity of ‘molten or figuid htoride Action of water “Approximate pit of aqueous solution of moderate ‘concentration ‘Nome Formate Structure Becireal 28 29Group VII: the halogens Atomic number [ Element | Symbol | Electronic configuration 9 Fluorine F 27 ” Chlorine a 28,7 35 Bromine Br 28,18,7 53 Iodine 1 28,18,18,7 All have seven outer shell electrons; they can easily attain the stable electronic configuration of the succeeding noble gas cither by gaining fan extra electron (from a metal) or sharing of electrons (with a non-metal). ‘Similarities and group trends (1) They ate all non-metals consisting of diatomic molecules which are formed by sharing one electron pair, eg. F-F, Cl, Br—Br, IL (2) The diatomic molecules are held together by weak van der Waals’ forces. Hence they are gases (Fz and Cz), volatile liquid (Bra) and volatile solid (Iz), with melting points and boiling points increasing down the group. (3) Being strong oxidizing agents, they are all chemically reactive. (@) On descending the group, the reactivity of the elements decreases. ‘This is because here the reactivity depends on the ease with which the halogen atoms gain electrons. That is, yt ee ri ‘This process becomes more difficult as the group is descended (large atom gains electron less easily). Hence oxidizing power decreases in the order: Fa(@) > Ch(@) > Ba® > LO Example 13.3 Group room WP nn vm m Or] ie 3 m| ite le [el [ol Fr | = ad{Na| Me | All si | P | Ss | a [ar an Ck Taw 230 (a) (b) fe) (d) fe) if) @) @) © @ ©) o With reference to the part of the Periodic Table given above, answer the following questions:~ Which group of elements consists of monatomic molecules? Why do they exist as monatomic molecules? Why do magnesium and calcium which belong to the same group have similar chemical properties? Why do compounds formed by the combination of group Il and group VII elements have higher melting points than compounds formed by the combination of group IV and group VII elements? Among the elements in the second period which is the strongest reducing agent and which is the strongest oxidising agent? In the third period, silicon and sulphur form compounds Sill and ‘SH respectively with hydrogen. A corresponding compound formed between phosphorus and hydrogen is PH,. What is the value of x? Does a given carbon atom always have the same mass as any other carbon atom? Explain your answer, (HKCEE) The Group VIII elements consist of monatomic molecules because they have either stable duplet or octet arrangement of electrons in their outermost shell, hence their atoms are stable enough to exist freely. Belonging to the same group (Group 11), both magnesium and calcium ‘have 2 outer shell electrons in their atoms. Both of them have the tendency to lose these 2 electrons to obtain the electronic structure of the nearest noble gas. Therefore they have similar chemical properties. Compounds formed by the combination of Group Il and Group VII elements are ionic compounds. The ions are held together in a giant lattice by strong ionic bonds. Compounds formed by the combination of Group IV and Group VIE elements are simple molecular compounds. In solid states, their ‘molecules are held together only by weak intermolecular forces called van der Waals’ forces. Since more energy is required to break loose the attraction in ionic than in simple molecular solids, the melting point of the former should be higher. Lithium, Li, is the strongest reducing agent and fluorine, F,, is the strongest oxidizing agent. xis3. No. This is because of the existence of Isotopes. Carbon has 3 isotopes, namely 'C, "°C and '*C. These isotopes are all carbon atoms, but with different number of neutrons and therefore different masses. 231Example 13.4 The data given in the table below refer to four elements in the same group of the Periodic Table. Flement | __Atomic number Bp. (°C) 4 37 688 B u 892 c 3 B17 D 19 74 (a) Rewrite the table so that the elements are in increasing order of ‘atomic number. (b) To which group in the Periodic Table do these elements belong? Give your reasoning. (c} Is this @ metallic group or non-metallic group? (d) What general trend is observed in boiling points on going down the group? What does this indicate? (e) What is/are the oxidation state(s) of these elements in their compounds? (f) Which element would be the most reactive, A, B, C or D? Why? (@) Blement Atomic number | _ Bp. (°C) c 3 1317 B u 892 D 19 m4 A 31 688 (b) Group 1. Electronic configurations of the elements C, B and D are 2,1, 2,81 and 2,88,1 respectively. They (and also element A) have 1 electron in the outermost shell of their atoms. (©) Metallic group (as there is only 1 electron in the outermost shell of the atoms). @ Boiling point of elements decreases down the group; this shows that metallic bond becomes weaker down the group, @ 4. (A. Reactivity of elements in a metallic group increases down the ‘group (or it has the largest atom and thus forms a uni-positively charged ion most easily). 232 EXERCISE 13 1) The graph below shows the variation in melting point for the first 20 elements in the Periodic Table; some elements are denoted by a letter (which does not correspond to its atomic symbol). 400 3000 2000 Metting point (K) 1000 Atomic number (@) If C is the lightest member of a group of elements known as the halogens, which other lettered element is also a member of the same group? (b) Select a lettered element which is (@_ an alkali metal (i) 2 Group IV element (i) a noble gas. (©) Comment on and explain the shape of the graph, with particular emphasis on the relevance of the term ‘periodic’ to describe he variation of melting point with atomte number. D sapstance | Melting | Boling | Electrical conductivity of : point (K)) point (K) ‘solid melt P| 365 463 ail nil a | 2156 | 276 nil nil R | 4323 | 2773 good good s__| 104 | 1680 nil 00d 233,Place P, Q, R and S in the appropriate categories from the following: (@) Giant metallic structure (b) Giant covalent structure (©) Giant ionic structure (@ Simple motecular structure 3) Elements 4, B, C, D belong to different groups in the same early period of the Periodic Table. It is piven that: 4,0 is a strongly basic solid; BCI, is aliquid; 0s can react with both acid and alkali; D produces an ion, D’. Answer the following questions using the above information. (@) Alllot the elements to appropriate groups in the Periodic Table, (b) What is the effect of an aqueous solution of 40 on red litmus paper? Explain, Write the structural formulae of the chloride and sulphate of A and predict their physical states under room conditions. (©) Write the empirical formulae of the oxides of B. What would you expect of their action on water? (@ Which of the following terms: acidic, amphoteric, basic or neutral should be used to describe C;0;? Write the empirical formula of the chloride of C and predict its action on water. (©) Write the structural formula of the compound formed between A and D. Predict its physical state under room conditions, and comment on the electrical conductivity of this compound @)_ at room temperature (ii) above its melting point. 4 Group tu un v vivilo 2nd El |e [H ard [Ae fel [ee San 7 stn [@ Ik ‘A part of the blank Periodic Table is shown above, Certain elements are indicated by letters which are not their usual symbols. In the 234 following questions, you should study the positions of these elements in the table and refer to the elements by means of the letters which have been given to them, (@) What is the most fundamental similarity among the members of a certain group? (b) Deduce from the table the atomic number of L. (©) What is the name of the family of elements of which OA GC Gi) Gu) J isamember? (@) Classify the elements into metals and non-metal, (©) Which of the elements s a transition element? (f) Which of the elements has the largest atomic size? (@) Which of the elements have a simple molecular structure? (h) What are the physical states of the elements at room conditions? @ Which of the elements can exist in two allotropie forms: one is very hard, the other can act as a lubricant? (@_ Which of the elements is the most electropositive metal among the ones shown? (&) Which of the elements is the most reactive non-metal? (® Which of the elements forms coloured hydrated ions? (m) Which of the elements form ions with two positive charges? (0) Which of the elements can react with cold water to form an alkaline solution? (©) Which of the elements forms amphoteric oxide and hydroxide? (p) Which of the elements do not form oxides? (@) Which of the elements form solid chlorides which are readily hydrolysed? (© Which of the elements forms a molecular chloride which will ‘not undergo hydrolysis? (©) How many moles of atoms of element J would you expect to react with 1 mole of atoms of element C to form a stable compound? (©) Which of the elements form covalent hydrides such that the atomic ratio of element to hydrogen is 1 : 1? (u) Which of the elements form oxides such that the atomic ratio of element to oxygen is 235@as @1:2 (ii) 21 2:3 (W) Write the structural formula and electronic formula of the compound formed between @ Bandl (i) Cand ii) E and G Gv) Band L. ((w) Suggest with reasons a possible shape and bond angle for @ molecule of the compound formed between F and I (Xx) Which of the elements is the strongest reducing agent? (y) Which of the elements is the strongest oxidizing agent? '5) The following table shows the atomic and ionic radi (in nm) of four elements which are in the same group of the Periodic Table, but rnot in the correct order Element Atomic radius Tonic radius P 0.099) 0.181 Q 0.064 0.136 R 0.133 0.216 s 0.114 0.195 Answer the following questions and give reasons in each case. (@) Which element would have the largest atomic number? (®) Is this @ metallic group, a non-metallic group, or a ‘mixed’ group consisting of both metals and non-metals? (©) Arrange the elements in the correct order in the group. (@) Which element would be the most reactive? (©) What is the trend in boiling points of the elements down the group? 66) Some information about the clement strontium, Sr, is given below: Atomic mass: 88 Electronic configuration: 2,8,18,8,2 Colour given by its compounds in flame test: Crimson Solubility in water of some strontium compounds: Chloride very soluble, hydroxide slightly soluble (4 g dm? at room temperature), sulphate and carbonate insoluble. (@) In which group of the Periodic Table should strontium be placed? 236 (b) What is the atomic number of strontium? (©) Is strontium a metal or a non-metal? (@) Write down the formulae you would expect for the chloride, hydroxide, sulphate and carbonate of strontium. These compounds are all of the same colour. What is the colour likely to be? (© What is the electron redistribution that takes place when strontium reacts with chlorine? () How many moles of electrons are redistributed in the combination of 176 g of strontium with excess chlorine? (®) How many faradays of electricity are needed to liberate 1 mole of strontium atoms during electrolysis? (h) Describe and explain what is likely to be observed when strontium is () heated in air (i) added to water (iii) added to dilute hydrochloric acid. (The mixture remaining from (h) (ji) is filtered, What would be obsrved when carbon dioxide is bubbled through the filtrate? Write an equation to show the change that takes place. @)_ The mixture remaining from (h) (i) is filtered. What would be observed when dilute sulphuric acid is added to this filtrate? Write an equation to show the change that takes place. (©) Which isthe stronger reducing agent, strontium or calcium? ® Compare the rate of reaction of strontium and calcium with water. () @ What is the approximate molarity of a saturated solution of strontium hydroxide at room temperature? Gi) Is this solution acidic, neutral or alkaline? 2371 HEAT OF REACTION & 4 BOND ENERGY EXOTHERMIC AND ENDOTHERMIC REACTIONS When a reaction occurs, the temperature of the reaction mixture often changes. ‘An exothermic reaction is a reaction that liberates heat energy: the temperature of reaction mixture is observed to increase. ‘An endothermic reaction is a reaction that absorbs heat energy: the ‘temperature of reaction mixture is observed to decrease, Example 14.1 State whether each of the following reactions (or changes) is exothermic or endothermic, (a) When a few drops of water are added to some calcium oxide on a white tile, steam is given out. (b) When a spatula measure of potassium iodide solid is added to a test tube half full of water and the mixture stirred, the tube becomes cold. (c) When a red hot coil of platinum wire (which has been heated in @ flame) is put in an atmosphere of oxygen and ammonia, the coit continues to glow red. (@) An exothermic reaction. (b) An endothermic change. (©) An exothermic reaction. HEAT OF REACTION ‘The HEAT OF REACTION is defined as the heat change when the number of moles of the reactants represented by the equation react completely. 238 Heat of reaction is denoted by AH and has the unit of kJ mot During an exothermic reaction, heat is lost to the surroundings; 4H for such a reaction is negative. During an endothermic reaction, heat isabsorbed from the surroundings; ‘AH for such a reaction is positive, Take the example of the following thermochemical equation re- presenting an exothermic reaction: CoHA(@) + Hh@) — CoH) AH = 138 Kd ethene ethane ‘This means that when 1 mole of ethene reacts completely with 1 mole of hydrogen to produce 1 mole of ethane, 138 kJ of heat will be evolved, Example 14.2 Given CoHalg) + Hal) —> Cyl) QH = ~138 kt Whar quatiy of heat would be given out when excess hydrogen reacts wid (a) 10moles of ethene _(b) 2.8 g of ethene? What minimum mass of ethene would have to be used 10 produce (c) 27.6 kd of heat (d) 552 kl of heat? (@) Heat evolved = 138X 10 = 1380 KI (b) Molar mass of C,H, = 28 g 28. 28 Heat evolved = 138 X 0.10 = 13.8 kd No. of moles of C;Hs used 0.10 (©) To evolve 138 KJ of heat, a minimum of 1 mole of C;H, should be used. To evolve 27.6 kJ of heat, number of moles of C,H, required - 27.6 = 1x28 = 020 Mass of CH, = 0.20 X 28 = 568 $52 og (@) Mass of GH, = 732 X 28 = 112g 239Example 14.3 The thermochemical equation for the reaction between zinc and dilute hydrochloric acid may be written as follows: Zn(s) + 2H'(aq) —+ Zn*"(aq) + Ha(g) OH (a) Is the reaction exothermic or endothermic? () How many moles of (i) zine (it) hydrochloric acid (HCl) have reacted when the heat change is ~150 kJ? fe) What would be the heat change if 3 moles of zinc were dissolved in excess dilute hydrochloric acid? (d) If the heat change were -120 ki, (i) what mass of zine would have dissolved in excess dilute hydro- ‘chloric acid? (ii) what mass of hydrogen would have been produced? (le) If dilute sulphuric acid were used instead of hydrochloric acid, how ‘many moles of this acid (HzSO4) would react if the heat change was ~150 kJ, excess zine being present? = 150 kd (@) The reaction is exothermic, as AH is —ve. (b) Number of moles of Zn = 1; number of moles of HCI (©) AH = 150 X 3 = ~450 15 (@) Molar mass of Zn = 65 g; molar mass of H = 2 g, 1 mole of Zn would react to give 1 mole of Hz, with evolution of 150 kJ of heat. When 120 kI of heat were evolved, 120 number of moles of Zn = 1X 45y = 08 number of moles of Hy = 0.8 (@ mass of Zn = 08X65 = 52g Gi) mass of Hy = 08X2 = 168 © If the heat change was —150 kJ, 2 moles of H’(eq) should be used, corresponding to 1 mole of HS0, ‘The heat of reaction is a very general term. Depending on the particular type of reaction, heat of reaction may be renamed and re-lefined, ‘Some examples are given below. 240 (1) Heat of combustion The heat of combustion of a substance is the heat change when 1 mole of it is completely burnt in oxygen, ‘The heat of combustion of methane, for example, is -891 KJ mot, CH,(@) + 202(@) —> CO2(g)+2H,0(@2) AH = ~891 kT Example 14.4 When 1.0 g of the gas ethane was bumt in excess oxygen, 52 kJ of heat were evolved, (a) Find heat of combustion of ethane. (0) Write the thermochemical equation for combustion of ethane. (@) Molar mass of ethane (C,H) = 30 12 mole of CH completely burnt in O; evolves 52 KI of heat; Tmole.....eee eee ee sx e0n = 1560 kJ Heat of combustion of C;Hy is 1560 kJ mot”. ©) CH.@) +4056) — 260,@) + 3100) air = -1560 Ks (not, 2C3He(@) + 702(@) —> 4C0,(8) + 61,02) OH=-3120 Kd, which refers to 2 moles of CH, being burnt) (2) Heat of neutralization ‘The heat of neutralization of an acid by a base is the heat change when 1 mole of water is produced from the neutralization, Acid Alkali Heat of neutralization (kJ per mole of water formed) HCI@q) NaOH(eq) 373 HNO3(aq) KOH(@q) 373 HNO, (aq) NaOH(eq) 373 H,80,(aq)___NaOH(aq) 648 CHyCOOH(@q) _NeOH(aq) 55.2 HF(aq) KOH(@q) 68.6 ‘The heats of neutralization of strong (Fully ionized) acids by strong alkalis are approximately constant and about —$73 KJ per mole of water 241formed, because the only change during neutralization is H'(aq) + OH (aq) —— Hf,0(®) — the other ions are just spectators and do not take part in the reaction. On the other hand, if a weak acid/weak alkali is involved, ionization of molecules must take place before neutralization can occur; thus another heat change called heat of ionization (which may be exothermic or endothermic) is involved and hence the total hheat change (heat of neutralization) is affected. ‘The energy change for strong acid — strong alkali neutralizations can be represented by the following energy level diagram: Haq) + OWGaa) Enerey 57.3 kd H,0@ Example 14.5 When 50 cm? of 2.0 M nitric acid react with 50 cm of 2.0 M potassium hydroxide solution, the temperature rise of the mixture is RC. State the temperature rise you would expect if (a) 2.0 M hydrochloric acid ts used in place of the nitrie acta (b) 2.0 M sodium hydroxide solution is used in place of the potassium hydroxide solution {c) 25 em? of 2.0 M nitric acid are added to 25 em? of 2.0 M potassium ‘nedroxide solution (d) 50 em? of 1.0 M nitric acid are added to 50 cm? of 1.0 M potassium hydroxide solution, 242 Give your reasoning in each case. (@) About 12°C. Nitric acid and hydrochloric acid are both strong acids. (b) About 12°C. Potassium hydroxide and sodium hydroxide are both strong alkalis. (©) 12°C. Half the volume of each solution is used, so half the quantity of heat will be produced. But since volume of the resulting solution will also be halved, the same temperature rise would be expected. (@) 6°C. Half the number of moles of each substance is used, s9 half the quantity of heat will be produced. Since volume of the resulting solution will be the same, temperature rise would be expected to be halved. BOND ENERGY It is found that a particular bond has a fairly constant bond strength in whatever compound it may be present. For example, the energy to break one mole of C—C bonds in ethane will be approximately the same as that required in propane, butane and so on. The average amount of energy associated with one mole of a particular bond is called its bond energy (unit: kJ mol"), In a chemical reaction, some bonds are broken while some new bonds. are formed, Bond-breaking processes are endothermic (i.e. absorb energy) ‘while bond-forming processes are exothermic (ic. liberate energy). The balance of these heat changes is the heat of reaction. ‘The approximate bond energies of some bonds are given below: Approximate bond energy (I mot) 435 431 414 464 244 498 347 ell 360 736 243Example 14.6 Calculate the approximate heat of reaction of the following reaction from bond energy values. 2H- Hig) + O=O(g) —* 2H-O-His) Energy change (kJ) 2 moles of H-H bonds broken 2X (4435) = 4870 1 mole of O=0 bonds broken 1X (4498) = +498 4 moles of OH bonds formed 4 X (464) =-1856 For the given equation, AH = +870 + 498 — 1856 = 488 kI Note: In bond-breaking processes, assign a 4ve sign to bond energies; in bond-forming processes, assign a —ve sign to bond energies. EXERCISE 14 Nore: Calculations on Heat of Reaction & Hond Energy ate not required by the TIKCE Chemistry syllabus. This exereise is optional 1) Given Cz Hs OH(@)+ 303(8) —+ 2CO;(g) + 3H,0(8) AH = -1370 ks, find the heat change when (@) 2 moles of ethanol are burnt in excess oxygen. (b) 4.6 of ethanol 2) 2C4Hio(g) + 1303(¢) —* 8CO,(g) + 10H,0(@) AH = 5720 ks (@) Calculate the heat of combustion of butane (CHto). (b) In order to produce 286 kJ of heat, what minimum mass of butane should be burnt? 3) When calcium carbonate is precipitated by adding @ solution of sodium carbonate to one of calcium chloride, the change may be represented by Ca?*(aq) + C05" (aq) — CaC05(6) AM = +12.6 KI @) Is the reaction exothermic of endothermic? What would be the heat change if (b) 0.2 mole of calcium chloride (CaCl,) was treated, in aqueous solution, with a slight excess of aqueous sodium carbonate (NaC, (©) 11.1 g of calcium chloride were similarly treated as in (b)? 244 | 44) Ammonia reacts with hydrogen chloride to form ammonium chloride and the reaction can be represented by the following energy level diagram, Nus(@) + HIG) Enerey “ina (a) Suppose 1 mole of ammonia was mixed with 2 moles of hydrogen chloride. Calculate the energy change which would lake place. State whether the change would be exothermic or endothermic. (b) When 1 mole of ammonia is dissolved in water to form a dilute solution, 35 kJ of heat are given out, Draw an energy level diagram to represent the change. 5) The following table gives the heats of combustion of a series of compounds called alkanes. Alkane Heat of combustion (kJ mol Methane Hy 890 Ethane CHSCHy 1560 Propane CH,CH;CHs -2220 Butane (CHs (CHa) CHs 2880 Pentane CH, (CH, )s CH ~3510 Hexane "Ha (CH jg CHa 4160 (@) Plot 2 graph of ‘heat of combustion’ against ‘number of carbon atoms per molecule’ (b) What would you expect the heat of combustion of the next member of the series, heptane CHs(CH; )s CH, to be? 4s(©) Another alkane has a heat of combustion of ~6780 kJ mol How many carbon atoms has this alkane per molecule? Write its formula, 6) Calculate the approximate heat of reaction of the following equations from bond energy values given in this chapter: (@) H-HG) + cg) — 2H-Cl@) ® nn HHHH id iii H-C-C-C=C-HG) + H-H@) — H-C-F-6-C-H) ha HHH 7) The heat of neutralization of sulphuric acid and sodium hydroxide is -64.8 KI per mole of water formed. (@) Write the thermochemical equation for the neutralization of sulphuric acid by sodium hydroxide. (b) How much heat is evolved when 25 cm? of 0.10 M sulphuric acid is added to 50 cm? of 0.20 M sodium hydroxide solution, neglecting any heat change due to dilution of the chemicals? 8) The bond energy values of C~C and N—N are 347 and 163 kJ mo! respectively. In the light of these data, explain why carbon can form fan enormous number of compounds in which carbon atoms join to fone another forming long chains, while nitrogen cannot. 246 RATE OF REACTION & EQUILIBRIUM 15 RATE OF REACTION Rate of a reaction is a measure of how fast the reaction proceeds. It ‘can be regarded as the rate of increase of concentration (or amount) of a specified product or the rate of decrease of concentration (or amount) of a specified reactant. Different chemical reactions proceed at different rates. For example, when aqueous solutions of silver nitrate and sodium chloride are mixed together, a precipitate of silver chloride is obtained immediately, whereas rusting of a piece of iron takes place very slowly, and may even take years to complete. Average rate and rate at a given instant Rate is usually nor uniform in the course of a reaction. Thus in stating rate of a reaction, we have to distinguish carefully 1, average rate over the whole reaction, or 2. average rate over a particular interval of the reaction, or 3. rate at a particular instant during the reaction. Study the following example. Example 15.1 When 0.36 ¢ of magnesium was added to 50 cm? of 1.0 M hydro- chlorie acid at room conditions, the magnesium reacted and disappeared in 90 seconds, ‘Mg{s) + 2HCW(ag) —> MgCls(aq) + Ha(s) (a) What was the average rate of the whole reaction expressed in terms of 247(i) rate of decrease of amount of Mg (mass in g) (ii) rate of decrease of HCI concentration (iti) rate of production of H, (volume in cm? at room conditions)? (b) Would you expect the average rate during the first I-minute interval to be the same as the average rate of the whole reaction? Why? (0) avenge ate of wt ection = 225 + 40 x 10° gs of Me ring Gi) According to the equation, 1 mole of Mg reacts with 2 moles of HCL. Noo moles of Me reacting pr second = 42% 10% Avenge ate of whol rectn 4.0 x 109 1000 24 X 2X “39 , = 6.7 X 10 mol dm” s" of HCI reacting (Assume volume of resulting solution to be SO cm*) (ii) 1 mole of Mg reacts to give 1 mole of Ha; ‘molar volume of any gas at room conditions = 24 000 cm* Average rate of whole reaction 40x 10? 24 = 4.0 cm* s of H, produced (at room conditions) x 24000 (©) No. Rate varies during the whole course of reaction. GRAPHICAL REPRESENTATION OF REACTION RATE A graph of the total quantity of 2 specified product against time generally has the form as shown overleaf: mB. i ts Time At the start of the reaction, no products are present, so the curve passes through the origin. The curve is steep at first, being approximately 8 straight line in the early stages of reaction; it becomes less steep with increasing time; finally it is horizontal. The point (B) at which the curve becomes a horizontal straight line indicates the finish of the reaction (time f2). ‘The slope of the chord between two points on the curve gives the average rate during that time interval in the reaction. For example, average rate of reaction from start to time fy is equal to slope of chord O4, ie ‘The slope of the tangent at a point on the curve gives the rate at that particular instant in the reaction. Thus the rate of reaction at time 1 is given by the slope of the tangent to the curve at point 4. This is = The tangent drawn to the point of the curve at time zero gives the initial rate, which is important in comparing the rates of ‘a reaction under different conditions, FACTORS AFFECTING RATE OF REACTION For a chemical reaction to occur, there must be collisions between particles of the reactants, Not every collision brings about reaction. In order to react, the colliding particles must possess a certain minimum amount of energy (called activation energy). Thus reaction rate is proportional to the number of ‘effective’ collisions per unit volume per unit time, 249Main factors which affect reaction rate are: (1) Particle size (surface area) of reactants ‘The rate of a reaction depends on the particle size of the reactants: the smaller the particles, the faster the reaction. For equal masses of small and large particles, the small particles have a greater total surface area and thus a greater chance for collisions to occur. (2) Concentration ‘An increase in concentration of reactants causes an increase in collision rate because the particles are more crowded together. Hence reaction rate is also increased. ) Pressure ‘An increase in total pressure of gaseous reactants (by compression) increases the collision rate because the particles are more crowded together, hence reaction rate is increased. Pressure has very little effect on volumes of solids and liquids, therefore pressure change does not affect reactions involving only solids and/or liquids. (4) Temperature As the temperature of a reacting system is raised, the average kinetic energy of particles in the system increases, causing the particles to move more quickly, and hence there isa higher collision rate; furthermore, a greater proportion of the particles possesses the required activation energy for reaction. Thus the frequency of effective collisions is increased, resulting in faster reaction rate (S) Catalyst A catalyst is a substance which alters the rate of a chemical reaction, but remains chemically unchanged at the end of the reaction, AA catalyst can function as such because it provides an alternative reaction pathway requiring different activation energy. (©) Light Light of suitable wavelengths can increase the rate of some reactions by providing the necessary activation energy for reaction, 250 Example 15.2 When a small piece of clean calcium is added 10 a beaker half full of water at room conditions, there is slight effervescence for the first ‘few seconds; the effervescence becomes more and more vigorous over a period of about half a.minute, and then diminishes in vigour, and eventually stops when the calcium disappears completely. Account for these observa. tions in terms of the factors which affect reaction rate. Calcium reacts with water according to the equation: Ca(@) + 2H,0(@) —> Ca(OH), (aq) + Hae) ‘The main factors which affect rate of this reaction are: (i) temperature (i) particle size (surface area) of the solid reactant (Ca). At the start of the reaction, the water is at room temperature. As the reaction is exothermic, more and more heat is liberated, speeding up the rate of evolution of hydrogen. But the size (and hence surface area) of calcium becomes smaller as reaction proceeds, producing an opposite effect. Reaction stops when all calcium has reacted. Example 153 A. student investigated on the rate of reaction between dilute sulphuric acid and zine 10 produce hydrogen and zinc sulphate. He added 1 g of granular zine to 50 cm 1 M sulphuric acid in a conical {flask and collected the hydrogen evolved in a syringe. He then repeated the experiment, varying only one factor at a time. Some possible ways in which the initial rate and the total volume of hydrogen collected may be influenced are shown below: Effect on initial rate Effect on total volume of hydrogen collected (i) unchanged unchanged (ii) unchanged increased (iti) unchanged decreased (iv) increased unchanged (v) increased increased (vi) increased decreased vil) decreased unchanged (siti) decreased increased (ix) decreased decreased Which set of effects would you expect in each case if the student made the following changes? Give brief reasons in each case. 251(a) Using 1 g of zine powder (o) Using 2 of granular zine (e) Using 50 cm? of 0.5 M sulphuric acid (d) Using 100 cm* of 1 M sulphuric acid {e) Increasing the temperature of the reaction mixture No. of moles of Zn in 1 g = oo1s 1 7 50 No. of moles of 180, in 50 cm? of 1 M H,S0s = 1X j555 = 0.050 From equation of reaction: Za(s) + HyS0s(aq) — ZnSO. (aq) + Ha(@) 0.015 mole of Zn reacts with 0.015 mole of HySOs, therefore 1,80, is in excess. ©) (iv). Initial rate is increased because of larger surface area of zinc (in form of powder). Volume of Hy formed is unchanged because the same mass of Zn is used. (©) (W). Initial rate is increased because of larger surface area of zine {a greater mass of Zn is used). HSOq is in excess and thus the seater mass of Zn used results in more Hz produced, (©) (ii), Initial rate is decreased because of lower concentration of H,SO, used. H.S0s is still in excess, thus volume of Hy formed is unchanged. (@) @. Initial rate is unchanged as the surface area of Zn(s) in contact with H2SOz(aq) is still the same, Zn is the limiting reagent and thus volume of Hy is unchanged in spite of an increase in amount of HSOs ©) (iv). Initial rate is increased because of increase in temperature. Volume of Hp formed is unchanged as there is no change in amounts of reactants. Example 15.4 The following graph shows how the rate of decomposition of a sumple of hydrogen peroxide solution varies with time (at room conditions). The initial volume of hydrogen peroxide solution was 100 cm? and 5 g ‘of manganese(IV) oxide were used as catalyst. The reaction was followed 252 by measuring the volume of oxygen evolved after given intervals of time. 2H;03(aq) —> 2H 0(2) + O2(s) 250) Volume of O3(em?) so °o 2 4 6 8 10 1214 16 18 20 2 ‘Time (min) (a) What was the maximum volume of oxygen obtained? (b) After what rime was the reaction complete? (e) What mass of manganese(IV) oxide would be left at the end of the experiment? Why? [d) How many moles of oxygen were formed when the reaction was ‘complete? fe) How many moles of hydrogen peroxide(H,0;) were present in ‘the criginal 100 cm? of solution? (f) What was the concentration of the original hydrogen peroxide solution in i) moles per dm? (ii) g perdm?? (g) What percentage of the hydrogen peroxide had decomposed after 4.0 minutes? (h) Comment on the shape of the graph. 253(@) Maximum volume of Oy obtained (read from graph) = 250 cm? (b) About 16 minutes. (©) MnO; is a catalyst and should be unchanged in mass, ie. 5 g of it would be left (@) Number of moles of 0, formed 250 _ 0.0104 34000 ~ (€) Since 2 moles of HzO; give 1 mole of O2, number of moles of HpO> that gives 0.0104 mole of O; = 0.0104 X 2 = 0.0208 (© @ Concentration of HO; = 0.0208 x 100 = 0,208 mol dm? Gi) Molar mass of H,0; = 34 g Concentration of Hs03 = 0.208 X 34 = 7.1 gdm” (@ From the graph, 192 om? of O, were produced aftr 4 minutes ‘When reaction went to completion, 250 cm? of 0, were produced. Percentage of 202 decomposed after 4 minutes = 2x 100m = 168% (h) The graph commences steply, and slowly levels off until it horizontal, This is bweause a8 reaction proceeds, the concentration of the reactant decreases, and hence the reaction rate becomes lower and lover; when all the reactant has turned into products, the rate of reaction becomes zero, EQUILIBRIUM Many chemical reactions are one-way or irreversible. For example, when 2 piece of zinc is added to excess dilute hydrochloric acid, all of it is converted into zine ions. Zn(s) + 2H"(aq) — Zn*(aq) + Hae) On the other hand, there are reactions which are two-way or reversible, and which do not finish completely. After a certain time, the reaction appears to stop but both reactant and product particles are present in the reaction mixture. This is so because the products can react to reform the reactants. We have a situation in which reactants are changing to products and products back to reactants, A “balance state’ or dynamic equilibrium is reached when reection is still going on, but with no apparent change taking place. 254 Let us consider the equation A+B # C+ D. ‘Two reactions are taking place, Forward reaction A+B —+ C+D Backward reaction C+D—> A+B ‘At constant temperature, the higher the concentration of reactants, the faster the forward reaction. Suppose we mix certain quantities of A and B. The rates of the forward and backward reactions will change as follows: Forward reaction Backward reaction At start rapid rate zero rate (concentration of (no material) reactants highest) As time passes | becomes slower as becomes faster as more ‘Aand Bare consumed | Cand D are formed and ‘and their concentrations | their concentrations decrease increase rate of forward reaction = rate of backward reaction (no further changes in properties of the system) Study the following graph: Reaction sate time needed to Tim Note that at equilibrium, the forward reaction and backward reaction are still taking place, but at the same rate; thus the equilibrium is dynamic, rot static 255Examples of reversible reactions are: H'(aq) + OH (aq) = H,0@) CH; COOH(®) + C;H; OH(2) * CH;COOC; Hs (2) + H, O(2) N20s(8) * 2NO;(e) Ni@) + 3H (8) + 2NHG@) 2802 (8) + Ox(s) + 280568) Fe(aq) + CNS(aq) [Fe(CNS)] (aa) 2Cr0."(aq) + 2H"(aq)——* Cr203" (aq) + H20@), BIC; (aq) + H,0@) + BIOCI(s) + 2HCI(aq) The following isa collection of some important terms. ‘An equilibrium system is a system which shows no change in pro- pertes with respect to time. Time to reach equilirhum is the duration from start to the instant after which no further apparent change occurs if there is no alteration in conditions Percentage yield of product is the percentage of the amount of product formed if the reaction went to completion. For example, if 1 mole of Np is mixed with 3 moles of Hy and the composition of equilibrium mixture is 0.9 mole of Ny, 2.7 moles of ‘H, and 0.2 mole of NHs, Ni(g) + 3H:(@) * 2NHA(@) At start To 0 (motes) At equiliorum 09 2.7 02 (moles) If the reaction went to completion, 2 moles of NH3 would be formed. Thus the percentage yield of NHy = 22 x 100% = 10% (ote: The petcntage by mole of NH inthe equi mine 02 © Uae27 400 * 10% = 538) A position of equilibrium is an intermediate stage in a reversible process at which no observable change is occurring. (Note that there ‘can be many positions of equilibrium for a particular system.) Changing position of equilibrium alters the percentage yield of product. If position of equilibrium shifts towards the right, more product 256 is formed, resulting in a higher yield. If position of equilibrium shifts towards the left, less product is formed, with a subsequent lower yield. LE CHATELIER’S PRINCIPLE. Le Chatelier's Principle states that if @ system at equilibrium is subjected to a change, the position of equilibrium will shift in such a way that reduces the effect of the change. EFFECTS OF VARIOUS FACTORS ON EQUILIBRIUM The table below summarizes the effect of change of concentration, pressure, temperature and addition of catalyst on rates of forward and backward reactions and position of equilibrium of an equilibrium system. Le Chatelier's Principle can also be used to predict the shift (of equilibrium position in each case. (Change in Rates of forward and : libris condition Backward reactions _| Position of equilibrium Tnerease of concentra- | increase of rate of shifts to right tion of reactant forward reaction Decrease of concentra | decrease of rate of shifts to right tion of product, backward reaction Increase of pressure in ‘gaseous reactions (by decreasing the total volume) 1) Number of moles | same increase in rates | no change same on both sides | of both forward and of equation backward reactions 2) Number of moles | increase of both rates | shifts to right of reactant greater | but forward rate | than tha: of product | increased more | 3) Number of moles | increase of both rates shifts to left of reactant less than | but backward rate | that of product eased more 257Increase in temperature | rates of both forward | for endothermic and backward reaction, equilibrium reactions increased, but | shifts to right; nnot to the same extent | for exothermic reaction, equilibrium shifts to left Catalyst rates of forward and | no change backward reactions increased or decreased to same extent (but time] to reach equilibrium is changed) Example 15.5 When bismuth chloride is dissolved in concentrated hydrochloric ‘acid, a clear solution is obtained in which the following equilibrium has been established: BiCls(aq) + HzO) * BiOCIs) + 2HCI(aq) (a) Comment on the position of equilibrium in the solution described above, (b) What would you expect to see on adding a lot of water to the solution? fe) What would you expect to see on adding concentrated hydrochloric acid t0 the solution? (@) The position of equilibrium in the solution described is well to the left. The solution is clear, showing that it contains mainly BiCls(aq) and H,0(@) (©) The clear solution would become turbid (white). (The position of ‘equilibrium shifts towards right.) (©) The solution would remain clear. (The position of equilibrium shifts towards the left still more.) Example 15.6 At room temperature, the gas ‘nitrogen dioxide’ actually consists of a mixture of dinitrogen tetroxide N,O., and nitrogen dioxide NO3, in dynamic. equilibrium: 258 N20alg! + 2NO2/8) pale yellow dark brown stopper gas syringe plunger ‘mixture of| 1N,0.(@) and NOs (@) The plunger of a gas syringe (containing 50 em? of ‘nitrogen dioxide” at room temperature) is pushed in quickly until the volume of gas is 20 em?, The plunger is held steady in this position. The brown gas has ‘an immediate darkening of colour, but quickly lightens slightly in the next few seconds. (a) Why does the gas have an immediate darkening of colour when the plunger is pushed in? [b) What does the lightening of colour in the next few seconds indicate? Explain the change in terms of changes in relative rates of the {forward and backward reaction and the position of equilibrium. (c) Show that Le Chatelier's Principle could be used to predict the results of the experiment. ‘The plunger of another syringe containing 50 cm? of ‘nitrogen dioxide’ is quickly pulled out until the volume of gas is 90 cm?. The plunger is hheld steady in this position. (d) What immediate change in colour intensity of gas occurs when the plunger is pulled out? fe) What happess to the colour intensity of gas in the next few seconds? (a) Since volume is decreased, concentration of gas is increased, resulting in an immediate darkening of colour. (b) Lightening of colour of gas indicates the formation of a new equilibrium mixture containing a higher concentration of pale yellow NzO.. In the equation N,Oq(g) * 2NO3(g), number of moles of gaseous reactant = 1, number of moles of gaseous product = 2. Before the system is disturbed, it is at equilibrium, with the forward and backward rates of the reaction equal. When the plunger is pushed in, volume of the system is decreased, resulting in an increase of pressure. Increase of pressure increases both rates, but the backward rate is increased more. Thus the system is no longer at equilibrium. 259‘As more N20.(g) is formed, the backward rate decreases, while the forward rate increases. This continues until 2 new equilibrium is established, with the two opposing rates equal again. When this happens, there is a higher concentration of N;O,(g) molecules than there was before. We say the position of equilibrium has shifted towards the left. (©) Since the pressure of the equilibrium mixture is increased, the system will adjust itself in such a way so as to reduce the pressure. For this to happen, the position of equilibrium must shift towards the left, thereby decreasing the number of gas molecules and hence the pressure exerted by them, (4) The gas has an immediate lightening of colour. (©) The colour becomes slightly darker in a few seconds, Example 15.7 100 Percentage of NHy 500 1000 Pressure (atmosphere) The graph shows the percentage of ammonia in the equilibrium ‘mixture obtained by reacting 1 volume of nitrogen with 3 volumes of hydrogen at different temperatures and pressures, oxides of iron being used as a catalyst, (a) Write an equation for the reaction, (6) What is the percentage of ammonia in the equilibrium mixture at 500°C and 250 atm? 260 (c) At what temperature and pressure does the equilibrium mixture contain the highest percentage of ammonia? 4) State whether the formation of anmonia is an exothermic or endothermic process. Explain. {e) State whether increased pressure will give a higher percentage yield of ammonia. Explain. (1) Considering your answers to-(b) and (c), explain why this reaction is operated at 500°C and 250 atmosphere pressure in many industrial plants. @) Nz@) + 3H) * 2NHyG) (©) 38% (1ead from graph) (©) 200°C and 700 atm. (@) It is an exothermic reaction, as increased temperature decreases the percentage yield of NHy (©) Increased pressure gives a higher percentage yield of NHy. As 4 moles of reactants would give 2 moles of product, if pressure is increased, the position of equilibrium will shift to right so as to reduce the effect of increasing pressure. (1) These are optimum conditions. Lower temperature would give a greater yield but time to reach equilibrium is too long. Higher pressure would increase yield but the cost for construction and maintenance of plant is too high. EXERCISE 15 RATE OF REACTION 1) $0.0 cm? of 0.0507 M sulphuric acid were added to an excess of freshly cleaned, granular zinc in a reaction vessel. The vessel was connected to a gas burette so that the hydrogen evolved by the reaction ‘Zn(3) + HS04(aq) — ZnSO, aq) + (8) could be collected and measured at intervals of time. The following table gives the results obtained. 261Vol. of hydrogen (em?) | 0 | 30 | 45 | 52.5 | $6.3 | $8.2 | 60.0 Time t (min) ofif2f3]4fsf{« Vol. of hydrogen (em?) | 60.4 | 60.6 | 607 | 608 | 60.8 | 60.8 Time t (min) 7[ 8[ 9 [1 fu [2 ‘The room temperature and pressure at the time of the experiment were 25°C and 760 mm Hg respectively (@) Plot the curve and explain its shape (Ie. why does it commence steeply, and slowly level off until it is horizontal”), (b) Show that the maximum volume of hydrogen obtained is in reasonable agreement with the volume you would obtain by calculation using the above equation. (©) By drawing a tangent to the curve, find the rate of reaction at the instant ¢ = 2 minutes. Express the answer as a rate of evolution of hydrogen (cm? min") under room conditions. Is this rate +tve or —ve? Why? 2) 25 cm? of 1.0 M hydrochloric acid were added to 30 g (a large excess) ‘of marble chips in a conical flask. The flask and contents were immediately weighed (on 2 top-pan balance) and a stop-clock was started. The total mass of flask and contents was noted as the reaction proceeded and the following table indicates the loss in mass at various times. Time (min) o [os | 10| 15 [20 | 30 | 40 Loss in mass(z) | 0 [0.119]0.219|0.294]0.350[0.431 [0.475 Time (min) 30 | 60 | 70] 80 | 90 [100[ 110 Loss in mass (g) |0.500|0.519| 0.525] 0.538 [0.538] 0.538 [0.538 (@) Plot a graph of ‘loss in mass’ against ‘time’ (b) Explain why there was a loss in total mass of reaction vessel and contents as reaction proceeded. (©) To improve accuracy of weighing results, the neck of the flask should be loosely plugged with cotton wool. Why? (@ Referring to the graph in (a), find the time taken when half the acid was used up. 262 (©) After what time was the reaction complete? () How long did it take for the second half of the acid to be used up? (@) Why did the second half of the reaction take longer time than the first half? (h) What mass of carbon dioxide had been evolved when the reaction was complete? (@_ How many moles of carbon dioxide were evolved? @_ How many moles of calcium carbonate (in marble) must have reacted in order to produce this number of moles of carbon dioxide? (k) How snany moles of hydrochloric acid were there at the beginning, of the reaction? (® Write an equation for the reaction between marble and hydro: 3) 05 g of manganese(IV) oxide was added to 50 em* of a hydrogen peroxide solution. The volume of oxygen gas liberated at room temperature and pressure was plotted against time as shown in the following graph. Volume of oxygen (en?)| ) 40] 44 T 23 4 § Time (miny (a) Consiger the points P, Q. R, S and T on the graph. At which point was the rate of reaction fastest? Why should the rate bbe fastest there? (b) Find the initial rate of the reaction. (©) What is the role played by manganese(IV) oxide in the reaction? 263,(@) If 15 g of the same manganese(IV) oxide were used in the ‘experiment, make a sketch of the graph expected in relation to the above one. (©) Draw a labelled diagram of the apparatus you could use for the experiment. 4) A student performs two experiments to study the reaction between (i) calcium and excess water and (i) calcium and excess hydro chloric acid. He uses 0.4 g calcium in both experiments and the volumes of hydrogen liberated at half-minute intervals are tabulated as shown below (all gas volumes are measured at s..p.):— Time (minutes) of os | 10] 15 | 20[ 25 a of 17 | 34] 76 | 134 | 184 Vol. of |Using water tytogen fem?) 2 44 | 182 | 207 | 222 using at. nc |°| ®8 | Time (minutes) 30 | 35] 40 | 45 | so y 222 | 224 | 224 Vo of |Using water | 216 | 220 eae fom} bs 24 | 224 | 224 vata ncy| 224 | 224 | 224 (a) Using “time” as the xaxis and “volume of hydrogen” as the y-axis, plot the results for each experiment on the same graph. Label the curves (i) and (ii). (b) Which reaction (i) or (i), has the greater initial rate? Why? (©) Which reaction () or Gi), has the greater rate at the moment of 2.0 time (minutes)? (@) When is calcium completely used up in each experiment? (©) Calculate the mass of calcium that will liberate 1 mole of hydrogen gas. (0. Why are the final volumes of hydrogen in (i) and (ji) the same? (C.D.C. Sample Question) 264 5) In a reaction between a solution made from compound xX and solution from Y, a gas is evolved. The reaction was performed three times with the following quantities of reactants. (@) 25 em? of 0.1 M X and 25 em? of 0.1 M ¥ solutions. (b) 25 em? of 0.2 MX and 25 cm® of 0.2 M ¥ solutions. (©) 25 em? of 0.2.M X and 25 em? of 0.1 M ¥ solutions. In each case, the volume of gas liberated at various times after the start was noted. The graph has 3 curves P, Q and R which summarize the 3 sets of results. Which of the above experiments is responsible for each curve? Explain how you arrive at your answer. ‘Volume of gas evolved (cm?) Time (minutes) 6) The reaction between sodium thiosulphate (NazS;0s) solution and hydrochloric acid is $10;? (aq) + 2H"(@aq) — $6) + $03(aq) + H,0(8). The time taken for @ definite amount of precipitate of sulphur to appear may be taken as an inverse measure of the rate of reaction. In each of six experiments, a volume (V cm) of a given thiosulphate solution was diluted to 100 cm? with water and then treated with 5 em? of 2.0 M hydrochloric acid. V (and therefore the thiosulphate concentration) was varied. ‘The time for @ definite amount of precipitate of sulphur to appear (¢ seconds) was noted in each case ‘The results were tabulated overlea: 265Vol. of thiosulphate (V cm?) 100 | 80} 60 | 40 | 30 | 20 Vol. of water added (cm* } 0} 20} 40 | 60 | 70 | 80 Time (t seconds) 33] 42] 54 | 76 {100 |178 TEx 10 = 30 [25 fies | 13 | 10 [56 (@) Plot a graph of V against 1. (V may be taken as a measure of the concentration of thiosulphate solution.) (b) Plot a graph of V against 1/t (1/t being a measure of reaction rate). From your graphs, what can you deduce about the relationship between reaction rate and concentration of thiosulphate solution? 7) Ammonium nitrite decomposes when heated: NH,NO, (aq) — 2H20(®) + Na(e) ‘The rates of decomposition of 25 cm? samples of ammonium nitrite solution were followed under three different sets of conditions. Graph | Molarity of solution | Temperature of solution °C) 4 050 5 B 050 85 c 02s 15 & A a Zz 5 2 2 Time (min) Draw one sketch showing all three curves, labelling each clearly. Explain briefly 266 EQUILIBRIUM 8) Describe the effect on the equilibrium position of the following reaction: N2Oe(g) * 2NO.(g) AH = 457.245 by (@) increasing pressure (by a decrease in total volume) (b) increasing temperature (c) adding a catalyst 9) Use Le Chatelier’s Principle to predict the effect of (i) increasing pressure (li) increasing temperature on (2) melting of ice [H,0() (arger volume) * H,0(®) AH > O] (@) the dissolution of ammonia in water (this change is exothermic) (©) the formation of sulphur trioxide from sulphur dioxide and oxygen (this reaction is exothermic). 10) What is the effect of increasing hydrogen ion concentration on the equilibrium position in each of the following: () 2Cr0,"(aq) + 2H"(aq) + Cr0;"(aq) + H20(®) (0) BiCls(aq) + H,0(@) = BiOCIG) + 2HCKaq) (©) Fe?"(aq) + CNS{(aq) * [Fe(CNS)]*"(aq) 11) Aqueous copper(II) ions react with aqueous ammonia to give tetcaamminecopper(Il) ions as illustrated by the following equation: Cu?(aq) + ANHs(aq) * [Cu(NHS)s]*(aq), ue deepblve What effect will the addition of dilute sulphuric acid have on the equilibrium position and how will this be shown in colour change? Explain your answer. 12) When some iron(II1) chloride is dissolved in distilled water, a clear orange-yellow solution is obtained. The solution is then boiled under reflux, and it slowly turns cloudy, due to the formation of a red-brown precipitate. FeCla(aq) + 3H20(8) + 3HCI(aq) + Fe(OH)s(6) (@) What is the red-brown precipitate? (®) Explain why you think it has appeared as a result of boiling ice. in what way has the equilibrium been disturbed? (©) What would you add to the cloudy mixture in order to re-obtain 267the clear solution? (a) Explain why dropwise addition of dilute sodium hydroxide solution to a solution of iron(Iil) chloride does not result in precipitation of iron(III) hydroxide until several drops have been added. 13) -2X(g) + ¥(g) = 22g) AH = —xkI ‘The above system is at equilibrium at temperature T and pressure P. (a) If the pressure is kept constant at P and the temperature increased, what will happen to (i the rate of the forward and backward reactions, (i) the equilibrium position of the system, (ii) the amount of Z? (b) If the temperature is kept constant at 7 and the pressure inereased, what will happen to () the rate of the forward and backward reactions, Gi) the equilibrium position of the system, Gi) the amount of 2? (HKCEE) 14) When hydrogen sulphide gas is bubbled into water and dissolved, it will ionize slightly as follows: H,S(aq) + H0(2) + H;O"(@q) + HS (aq) HS"(aq) + H,0(8) = HyO%@q) + S*(aq) When excess hydrogen slphide is bubbled into aqueous solutions ‘of the following metal ions under different conditions, the following results are obtained: ‘aq, solution made ‘aq. solution made acidic by dilute aq, solution | alkaline by HCl NHs(aq) + NH4Cl(aq) K°_| no ppt. no ppt. no ppt. Zn** | no ppt. dirty white ppt._| dirty white ppt. PB | dark brown ppt. | dark brown ppt. | dark brown ppt. Gu" [black ppt. black ppt. ‘lack ppt, (a) Using Le Chatelier’s Principle, explain all the above observations. Write equations where applicable. 268 (b) Describe how you would purify a solid sample of zine chloride contaminated with copper(I) chloride using hydrogen sulphide as. 15) Bthyl ethanoate can be made from ethanoie acid and ethanol according to the following equation: CH;COOH) + C;HsOH(® * CHCOOC, Hs(®) + H:0() ethanole ‘ethanol ethyl water acid ethanoate (@) In the above reaction, concentrated sulphuric acid is added as ‘catalyst. Besides this, what further use does it have? (b) If 1 mole of ethanoie acid is added to 1 mole of ethanol, then at equilibrium, what is the number of moles of ethyl ethanoate formed? (©) What is the effect of pressure change on this reaction? Why? (@ This reaction is best performed using pure ethanoic acid and pure ethanol instead of using their dilute aqueous solutions. Explain, 16) Propanoic acid, a weak organic acid, ionizes in aqueous solution to sive the following equilibrium system: CH3 CH, COOH(aq) + H,0(2) + CH;CH;,COO (aq) + H30"(aq) (@) What can you tell about the position of equilibrium of a 2 M propanoic acid solution system? (b) Suggest a reagent which, when added to an aqueous solution of propanoic acid, would be effective in shifting the equilibrium to the right. Give the reason for your choice. (©) Describe briefly how you would convert sodium propanoate to propanoic acid in the laboratory. Explain the underlying principle (@) The pH of @ 2 M solution of propanoie acid is found using pH paper. Explain any change in pH¥ of the acid solution on adding solid sodium propanoate. 17) Iron( Hil) ions react with colourless thiocyanate ions CNS” to form ‘complex ions of formula [Fe(CNS)]?*. The reaction is reversible: Fe™(aq) + CNS{(aq) = [Fe(CNS)]”* pale yellow colourless 0d In one experiment, 10 cm? of 0.007 M iron(II1) nitrate solution 269‘were mixed with 10 cm? of 0.007 M potassium thiocyanate solution. Equilibrium was quickly established. ‘The equilibrium mixture, X, was pale red in colour. ‘The following operations, (a) to (e), were carried out on separate portions of X. (a) A few crystals of iron(III) nitrate were added to X and the solution stirred. (b) A few crystals of potassium thiocyanate were added to X and the solution stirred. (©) Half a spatula measure of sodium phosphate was added to X and the solution stirred. (@) A few crystals of potassium nitrate were added to X and the solution stirred. (©) Excess concentrated sodium hydroxide solution was added to X. The solution was then filtered. State and explain what you would expect to see in each operation. 18) Consider the reaction: 280.(g) + Or(g) * 2803(8) AH = ~197kI (@) How does the rate of the forward reaction compare to the rate of the backward reaction at equilibrium? (b) What is the effect of adding some additional O2(g) after the system has reached equilibrium? (©) If the pressure of the system is increased by reducing the volume (other conditions being kept constant), how will the equilibrium position shift, and what further effect will this have on the $0s(g) concentration? (@ What effect should increasing the temperature have on the equilibrium position if pressure remains constant? (©) What effect does a catalyst have on the rate of the forward reaction? (© What effect does a catalyst have on the rate of the backward reaction? (g) Compare the equilibrium concentration of SO3(g) without a catalyst to the equilibrium concentration of SOs(g) with a catalyst. Explain. 270 1 6 SOLUTION PATTERNS & SOLUBILITY INTRODUCTION Polar covalent bond It has been mentioned in Chapter 2 that covalent bond may incorporate some ionic character. For example, the bond in hydrogen chloride molecule (°*H—CI*") is not purely covalent and can be described as a polar covalent bond. Polar and non-polar molecules ‘A molecule (uch as *H—CIP) having 2 opposite electric poles (6+ and 8) is described as polar; a molecule (such as 1-1) with no such separation of charge is described as non-polar. The overall polarity of a molecule is determined by the polarity of covalent bonds, number and position of lone pairs and shape of the molecule. (A detailed account of this isnot to be given here.) Examples of non-polar molecules are: iodine (I), hydrogen (H.), nitrogen (Nz), chlorine (Cla), methane (CHa), tetrachloromethane (CCly), benzene (CoH), hexane (C,Hy4), carbon dioxide (COs) etc. Examples of polar molecules are: hydrogen chloride (HCI), water (H,0), ammonia (NH;), ttichloromethane (CHCIs), ethanol (C;HsOH), seston (CHyCCH) ee i ° Example 16.1 Given the substances: fa) water (b) sodium chloride (c) iodine (d) tetrachloromethane (e) ethanol (f) ammonium chloride mlace each of them in the appropriate category from the following: (i) ionic compound (ii) simple molecular campound consisting of non-polar molecules (iii) simple molecular compound consisting of polar molecules iv) element consisting of non-polar molecules Give your reasoning in each case. (@) Water is @ simple molecular compound consisting of polar molecules. ‘A water molecule is V-shaped: QP — Ione pair aN wo It has 2 polar ®“O—H" bonds and 2 lone pairs. The effects due to the polar bonds and lone pairs do not cancel out, thus the molecule is polar. (b) Sodium chloride is an ionic compound consisting of Na” ions and CY ions (©) Iodine is an element consisting of non-polar molecules. Each I-I molecule has 1 non-polar bond. (@) Tetrachloromethane is a simple molecular compound consisting of non-polar molecules. ‘A tetrachloromethane molecule has regular tetrahedral shape: a 1 is a aN, It has 4 polar 5C—ci bonds and no lone pair. Because of the symmetry of the molecule, the effects due to the 4 polar bonds cancel out one another exactly. Thus it is non-polar. ©) Ethanol i Bach ethanol molecule has 5, slightly polar C—H bonds, 1 non-polar C=C bond, 1 polar °*C-0% bond, 1 polar 0-H" bond, and ‘two lone pairs on oxygen. The effects due to the polar bonds and lone pairs do not cancel out, thus the molecule is polar ple molecular compound consisting of polar molecules. (© Ammonium chloride is an ionic compound consisting of NH," ions and CT ions om Intermolecular forces Weak forces of attraction always exist among molecules. These forces are much weaker than chemical bonds (eg. ionic or covalent bonds), and they are called intermolecular forces. Three main types are: (1) Dipote-dipole attractions 2) Van der Waals’ forces (3) Hydrogen bonding. Dipole-dipole attractions Polar molecules are permanent electric dipoles. There are dipole-dipole attractions (attractions between dipoles) arising through electrostatic forces, between opposite charges. Polar molecules (¢.g. CHCl;) tend to orientate as shown in the following diagram, and as a result, attractive forces develop between the molecules. Spy & Hae Chemists have found that weak attractive forces exist between all atoms and molecules. It is easy to see that such forces exist between polar molecules (eg. trichloromethane), but there are weak forces also between non-polar molecules. These forces are known as van der Waals’ forces. The weak short-range forces of attraction, independent of normal bonding forces, which exist between atoms and between molecules in the solid, liquid and gaseous states are known as van der Waals’ forces. Van der Waals’ forces are considered to be due to momentary dipole.induced dipole interactions between molecules (or between atoms). The momentary (temporary) dipoles arise because the electrons in 4 molecule are in a continual motion. At any particular instant, the electron charge cloud in a molecule may not be perfectly symmetrical, that is, there is more electronic charge on one side of the molecule than 273the other. This means a momentary (temporary) dipole is set up. This dipole induces a dipole in neighbouring molecules, and attractive forces result, momentary induced Alipole dipole Obviously, these dipoles are not permanent, as they continue to arise and disappear all the time; but the forces between the original dipoles and the induced dipoles are always attraction. Therefore at any time, there will be attractive forces between molecules. In general, the greater the number of electrons in a molecule and the more weakly they are held by the nucleus, the more easily can the momentary dipoles (and hence the induced dipoles) be formed, and the greater will the van der Waals’ forces be between molecules. Hydrogen bonds Hydrogen bonds are extra strong intermolecular attractions existing between hydrogen atom of one molecule and the lone pair of a highly electronegative atom of another molecule. ‘The essential requirements for formation of hydrogen bonds are: (A substantially 5+ hydrogen atom attached to a highly electronegative atom (usually F, 0 or N only ~ the three most electronegative elements). (i) A lone pair on an electronegative atom (again F, O or N) to provide a region of negative charge. It is important to note that between given molecules, more than cone type of intermolecular force may be present at the same time. For example, molecules which are hydrogen-bonded will also be attracted by dipole-dipole attractions and van der Waals’ forces. Example 16.2 Draw a diagram to show hydrogen bonding in each of the following: (a) Water (b) Ammonia (¢) Ammonia water 274 @ bydiogen bond 4 nen No lot om 2, HW — 4H lone aie (b) H H H H H H © # 4 H 1 I RN-H- + $Q-H s+ EN-H i H H H Example 16.3 Arrange the compounds in each of the following groups in the order you would expect for their boiling points, putting the one with the lowest boiling point first. Explain how you arrive at the order. (a) AW iH HHHH HHH pbben, otnebbe bawdy re bik H-C-C-OH , H-C-C-C1 , H-C. é on ot tt atte utets yak ee AES aes 275Since all of the compounds are non-polar, they have only van’ der Waals’ forces among molecules. But as molecular size increases, van dder Waals’ forces also become stronger, thus the above order follows, ) HH HH 4H natab-n < H-b-C-a < H-€-€-oHF in boing pin a a Although all of the compounds have two carbon atoms in a molecule, the intermolecular forces are different in each of them. ClHy=CH, is a non-polar compound, with only weak van der Waals’ forces among the molecules, CHsCH,C1 is a polar compound with dipoledipole attractions as well as van der Waals’ forces among molecules CH3CH,OH is a polar compound with dipole-dipole attractions, van der Waals’ forces and also H-bonds among molecules. Thus the above order follows. SOLUTION PATTERNS AND SOLUBILITY Some defit ‘A solution is a homogeneous (uniform) mixture of two or more substances. A solution may consist of a solid and a liquid (e.g. salt and water), 2 gas and a liquid (e.g. oxygen and water), a liquid and another liquid (eg. alcohol and water), a gas and another gas (e.g. oxygen and nitrogen), or even a solid and another solid (eg, alloys of metals). tions An aqueous solution isa solution of a substance in water. ‘The name solute is usually given to the substance present in smaller amounts and the name solvent to the other. A solute is the dissolved substance. A solvent is the substance which dissolves a solute. Solution patterns Many chemical reactions occur in solution; an understanding of solution patterns is therefore important, especially that of solid (or liquid) in liquid solvent. 276 A DS In general, ‘ike’ would dissolve ‘ike’. That is, non-polar liquids are usually “good solvents for non-polar substances (elements or simple ‘molecular compounds consisting of non-polar molecules), and polar liquids are usually good solvents for polar substances (ionic compounds cr simple molecular compounds consisting of polar molecules). Take the example of dissolution of iodine in tetrachloromethane. fodine molecules (1,) are held to one another by van der Waals’ forces, and tetrachloromethane (CCl) molecules are attracted by the same type of forces. Both of these are similar in magnitude to the van der Waals’ forces that would be set up among iodine and tetrachloromethane ‘molecules. Thus it is easy for tetrachloromethane molecules to penetrate into iodine crystals and to separate the iodine molecules; similarly, it is easy for iodine molecules to separate the tetrachloromethane molecules, and so distribute themselves throughout the liquid. It should be noted that some simple molecular compounds (eg. CHsOH, CH,COOH) are soluble in water because their molecules would form hydrogen bonds with water molecules. Example 16.4 State whether each of the following is soluble in water (a polar solvent) or tetrachloromethane (a non-polar solvent) or both: (a) sodium chloride (6) iodine (c) ethanol (d) ammonium chloride (e) hydrogen chloride (f) hexane CHa (g) acetone (h) octan-1-0l CH(CH,), OH (2) NaCl is soluble in water only (b) 1 is soluble in tetrachloromethane only. (©) C;HsOH is soluble in both, (@) NH,Clis soluble in water only. (©) HClis soluble in both, () CHhs is soluble in tetrachloromethane only. (@) (CH5),C0 is soluble in both, (h) CH (CH, ); OH is soluble in tetrachloromethane only. Note: (1) The descriptions ‘soluble’ and ‘insoluble’ used here are only Telative terms. For example, in the case of (b), when iodine crystals are shaken with water for some time, a pale yellow solution is formed, showing that iodine is actually very slightly soluble in water. 2772) Am ethanol molecule or octan-I-ol molecule is made up of 2 parts (® the non-polar hydrocarbon part which tends to stay away from water and i) the highly polar OH group which tends to dissolve in water by forming hydrogen bonds with its molecules. Ethanol is soluble in water because the ‘wateroving’ —OH group exerts a greater influence than the ‘waterating’ hydrocarbon part (C Hs). ctan-I-ol is insoluble in water because the hydrocarbon part (CH,(CH,),—) is so large that its effect dominates, of solids in water Water is the most common solvent. We are now going to consider the solubility of a solid in water. ‘There is a limit to the amount of solfd which can dissolve in a fixed mass of water. A saturated solution of a solute at a particular temperature is one which can dissolve no more solute at that temperature (in the presence of undissolved solute). The SOLUBILITY of a solute in water at a particular temperature is the amount (in g) of solute required to saturate 100 g of water at that temperature. (ote: The phrase concerning temperature must not be omitted from the definition because solubility is temperature-dependent.) Example 16.5 In an experiment to determine the solubility of ammonium bromide (NHgBr) in water, the following results were obtained: ‘Mass of evaporating dish = 25.258 ‘Mass of dish + saturated solution at 20°C = 42.72 ‘Mass of dish + solid NH, Br after = 32.728 evaporation to dryness Calculate the solubitty of ammonium bromide in grams per 100 g of water at 20°C. 278 Mass of NH,Br = 32.72 — 25.25 = 747g Mnsofeatr = #2723272 = 1008 So at 20°C, 10.0 g of water can at most dissolve 7.47 g of NH,Br, 100 gof ater would atmos ds 7.47 x 120g = 74.73 of NH,Br. Solubility of NH, Br at 20°C = 74.7 g per 100 g water. Effect of temperature on solubility In general, the solubilities of solids in water increase with ise in temperature. However, a few exceptional solids (eg. calcium sulphate and calcium hydroxide) and all gases are less soluble in hot water than in cold. The solubilities of some compounds (e.g. sodium chloride) change little with temperature. A solubility curve is a graphical representation of the variation of solubility with temperature. Usually, the vertical axis represents solubility and the horizontal axis temperature. The value of solubility at a particular temperature can be read from the graph. ‘The following is a graph showing the solubility curves of a few salts Solubility ing per 100g water Ey 0 6 30 100 ‘Temperature in °C 279EXERCISE 16 1) In which of the following liquids would you expect iron(II1) chloride to be soluble? (a) Methylbenzene (C7Hs) (b) Water (©) Ethanol! (@) Acetone (©) Hexane (Calis) (©) Tetrachloromethane 2) Given the formulae of some compounds, arrange them in the order you would expect for their solubilities in water, putting the ‘most soluble one first. Give your reasoning. eur ot hin f ©) HH @ HHHH n-¢-ta w-c-¢-¢-t-on uh haan 3) Given the formulae of three compounds, arrange them in the order you would expect for their solubilities in tetrachloromethane, putting the most soluble one first. Give your reasoning. (@) 1,0 ob © Kel 4) The solubility of iodine in a liquid X at 25°C is 10 g per 100 g of solvent, and its solubility in water at 25°C is 0.02 g per 100 g solvent. fodine forms a violet solution when dissolved in X and @ pale yellow solution when dissolved in water. (@) Compare the solubilities of iodine in X and water at 25°C (b) From the answer in (a), would you expect water and X to mix or would you expect them to form two separate layers? Explain your reasoning, (© A pale yellow solution of iodine in water is shaken with an equal volume of X. Describe what you expect to see after shaking the mixture for several minutes and allowing it to stand. (@) Would you expect iodine to be soluble in heptane (Cz Hi)? Explain your reasoning 280 5) 26 g of a saturated solution of a salt in water was prepared at 25°C. It was then evaporated to dryness giving 6 g of salt. What is the solubility of the salt in water at (a) 25°C (b) So°C? 6) The results of an experiment to determine the solubility of potassium chlorate(KCIO,)) in water at 17°C were as follows: Mass of dish 20.35 g Mass of dish + saturated solution of KCIO, at 17°C = 31.35 g Mass of dish + solid KCIO, after evaporation = 21.35 ¢ to dryness (a) Calculate the solubility of potassium chlorate in grams per 100 g of water at 17°C. (b) What would be the mass of a saturated solution containing 50 g of water, also at this temperature? 7) The solubility of a substance at 20°C is known to be 25 g per 100 g of water, What mass of the substance is present in 100 g of its saturated solution at 20°C? (HKCEE) 8) By referring to the graph given, answer the following questions: Solubility ing solu per 100 ¢ water ‘Temperature in°C 281282 (@) At what temperature do sodium chloride and potassium chloride have the same solubility? (&) What mass of crystals will be deposited if 300 g of potassium chlorate solution, saturated at 52°C, is allowed to cool to 23°C? (©) A mixture of 40 g of sodium chloride with 40 g of potassium chloride is added to 100 g of water and heated to 50°C. How much solid remains undissolved? (HKCEE) 1 7 NAMING OF ORGANIC COMPOUNDS INTRODUCTION In naming an organic compound, very often we have to know its structural formula frst. This is because for a given molecular formula, there may be several different structures possible. Compounds having the same molecular formula but different structural formulae are called structural isomers. For example, the molecular formula C,H, corresponds to two differert compounds, the structural formulae of which are shown, below: [As can be seen above, the structural formula of an organic compound expresses the kind, number and also the arrangement of atoms in one molecule of the compound (every bond is shown in the formula). In some instances, however, it would be desirable to write the shortened form of structural formula, in which only the arrangement of constituent groups in the molecule is shown, but not the disposal of each individual ‘atom, For example, for pentanoic acid, the detailed form of structural formula is: HHH HO tile H-C-C-C-C-0-0-H ieee HHHH ‘while the shortened form would be CH3(CH, )s COOH. Since the shortened forms of structural formulae are so often used, it is important to interpret correctly the shortened forms of various groups. 283,eg. Detailed form H-C~ 1 H HHH HOCH, I —c=¢- (Note that carbon-carbon in the shortened form) 284 ‘Shortened form CH — —(CHa)s— ct, —CHCH; — (or ~CH(CH3)CH; ~) e -COOH COOR —CHO (not ~COH) CHy —CH=C— (or ~CH=C(CH,)-) double or triple bond must be shown even Mistakes in deriving the correct structures from shortened structural formulae can be avoided by remembering that each carbon atom has four and ‘only four bond pairs in neutral molecules. Take the example of —COOH ‘group: if its structure was written as -C-O—O-H, the carbon atom would have only 2 bond pars — this way of writing is therefore incorect. " ‘The correct structure is -C-OH, in which the carbon atom has the correct ‘number of bond pairs (ie. 4). For organic compounds, there are two types of names possible: I. Nonaystematic names (trivial or common names) IL, Systematic names (the IUPAC names) Note: TUPAC stands for International Union of Pure and Applied Chemistry. ‘The IUPAC system of naming has the advantage that by following certain rules, an unambiguous name can usually be assigned to a given structure ‘The trivial names, however, have no direct connection with the corresponding molecular structures. For example, the name chloroform suggests that there is chlorine in the compound, but the number of chlorine atoms (and also other types of atoms) in the molecule cannot be predicted just from the name Therefore, the IUPAC system of naming should be adopted whenever possible, although for some compounds, trivial names are more commonly used (¢.g. for chlorophyll, the IUPAC name is almost impossible to assign). IUPAC SYSTEM OF NAMING For the sake of convenience in discussion, organic compounds are divided into the following types: (A) Alkanes (B) Unsaturated hydrocarbons (alkenes alkadienes ete.) (©) Compounds containing non hydrocarbon substituents. (A) ALKANES. Alkanes are *saturated open-chained (i.e. not cyclic) hydrocarbons of general formula CaHan¢2 (common name: paraffin). 4 saturated hydrocarbon is one which does not contain carbon-carbon double bond oF triple bond. 285‘The names of alkanes all end in -ane, e.g. methane, ethane etc. From the fifth member onwards, the names begin with the Greek prefix for the number of carbon atoms in the chain, eg. pentane (Cs), hexane (Ce) et. Names of some straight-chain (ic. unbranched) alkanes are shown below: ‘Mumber of caer eT yy | Molecular formula | Structural formats | Name 1 cu, ch, Methane 2 CoH CHCl Ethane 3 Calls CHCHCHs Propane 4 Coo CHS(CH;)2CHs | Butane s Callie CH(CH)SCHs | Pentane 6 CHa CHS(CH.)CHs | Hexane 1 Cole CHy(CT,ISCHs | Heptane 8 Cathe CHy(CH,).CHs | Octane 9 Colao CHy(CH,);CH, | Nonane 10 rota CHS(CH, ICH; | Decane Alkyl groups (represented by R—) Alkyl groups are derived from alkanes by removal of a hy drogen atom. ‘They are named by replacing the ending -ane of the parent alkanes by -yl. eg. Alkane CylHan42 Alky group Cyltan+1 —(0rR~) CH, methane CH; ~ methangyl ie. methyl CH,CH, ethane CH, CH, ~ ethyl CH,CH,CH, propane CHsCH; CH, — propyl and so on, So far we have been concerned only with straight-chain alkanes and radicals; for branched-chain alkanes, the following IUPAC rules apply. bs bn bed CH 286 (Note: This seemingly very complex structure is purposely chosen to illustrate the common IUPAC rules; at F.5 level, the compounds met would be much simpler.) Steps taken: 1) Select the longest continuous main carbon chain. With reference to the above formula, the longest continuous main carbon chain consists of 10 carbon atoms and the compound is considered to be derived from it (decane). cH cit, crc, b,c, -¢—a, ct, -cr Gy dy, Gr-oy eu, 2) Recognize the ‘substituents and number the carbon atoms (1.2.3 onwards) in the chosen main chain. The numbering should start from ‘the end such that the smallest value is assigned to the lowest-numbered substituent. Tn the example here, © Ob GO + Go Low ~C-CHh, C—O CH CH cHy CH, CH-CHy, oH, ‘when we number in direction (i), the lowest-numbered substituent will be attached to C-4 (ie. the fourth carbon atom), while in (), itis C3 (‘e. the third carbon atom). Hence direction (i) is chosen. CH, CHy I 2 0 Cm" CH, CH, ~~-CHy I iy! cH; "CH-"CH, I CHy +A substituent refers to any atom (except hydrogen) of group attaching to a carbon atom, 2873) Assign to each of the substituents a name and a number. In the present example, they are named as 3-methyl, 3-methyl, S.methyl, S-ethyl and 7-methyl 4) If several substituents are the same, they should be grouped together and named with a multiplying prefix, such as di (for 2), tri For 3), tetra- (for 4) etc., but the numbers of the attaching carbon atoms have to be all written dow. In the present example, the various methyl groups are grouped together and named as 3,3,5,7-tetramethyl (not 3,5,7etramethyl or 3,3,5,7- methyl ete.) 5) Arrange the names (with the numbers) of the substituents in alphabetical order (independent of the numbering), and join them as prefixes to the main chain name, eg. ethyl before methyl, methyl before propyl etc. (Note: Dimethyl, trimethyl and tetramethyl are all regarded to start with m) In the present example, the name is thus alkyl groups as prefixes main chain name 4Sathyl3,3,5,tetramethyldecane no hyphen hyphens ‘ot 2 separate words Note: Numbers are inserted between hyphens (except at the beginning of a name); two or more consecutive numbers are separated by comma(s). Example 17.1 a, GH, Give the IUPAC name to CH,CH,~*C-CHy aly 6 (CH, CCH, By following the rules indicated above, the readers should be able to get the answer: 3-ethyl-3-methylhexane 288 Example 17.2 CH, CH i i Give the IUPAC name to CH; ~C——C-CH; ~C-CH al 1 ees tH ‘The answer is 23,5-trimethylhexane. Note it cannot be named as 2,4,5-rimethylhexane. Look at the formula below: — H Ch H oH CH H woah gh al al gl us co Ca fom Coy fa- Cay“ i i HOH Ch HOH HO The lowestsnumbered substituent is 2 no matter ftom which end we start numbering, so we have to choose the way that gives a smaller sum. Because 2434+5<2 +445, the name follows. To convert a name to a structure Steps taken: 1) Examine the name to find length of the main carbon chain. Write the main carbon chain without bothering about hydrogen atoms. 2) Indicate side chains by attaching the appropriate number of carbon atoms to the correct places in the main chain, 3) Complete the structural formula by adding the necessary number fof hydrogen atoms (noting that each carbon atom has 4 and only 4 bond pairs). For the example 4ethyl-2-methyloctane, steps taken are: write main chain only number the main chain and attach side chains 289Bee gM nen a add H-C—C—C—C—€-€-€-€-H hydrogen ro atoms HH-C-HHH-C-HH HOH I H | H-C-H H (or inshore, CH, CHCH, CHCH, CH CH CH) CH, CH CH, (B) UNSATURATED HYDROCARBONS. If a hydrocarbon has C=C double bond and/or C=C triple bond, it is said to be unsaturated, Openchained hydrocarbon with only one C=C double bond is called alkene (general formula: C,Haq; common name: olefin); if there are wo, itis alkadiene; if three, alkatriene and so on, In the following account, only naming of alkenes will be considered. Naming of alkenes ‘The above discussed IUPAC rules for naming alkanes still apply here, with some further points to note: 1) Choose the longest continuous main carbon chain including the double bond. 2) Systematic names are derived from the alkanes by replacing ane by 3) Unsaturated centre (C=C bond) has priority over alkyl groups in selection of main chain and direction of numbering (illustrated by Examples 173 and 174). 290 Example 173 Give the IUPAC name to H | HoH H H H H H-C-H H shoal ost ah gh gh gt \ ae fo~ fo- Co= Co)~ vo fo "Ca fon HOW HoH HH direetion (i) — “+ direction (ii) Since unsaturated centre has priority over alkyl group, the correct direction will be the one which gives the smallest number to the unsaturated centre (although an even smaller number can be assigned to the alkyl group in the other dizection). In direction (j), the unsaturated centre is between C-3 and C-4, while in (ji), it is between C-5 and C4. Therefore direction (i) is chosen. Hence the name is: Tmethyloct-3-ene alkyl group main a carbon-carbon double bond between C3 and as prefix chain the next higher carbon atom ie. between C-3 name and C4 (not 2-methyloct-5-ene) Example 17.4 Give the IUPAC name to 21Chain (a) with direction of numbering as shown is chosen. This is the longest carbon chain including the double bond. The direction of numbering is selected so as to give the smallest number to the double bond. Therefore the name is 2-ethylpent-1-ene, Example 17.5 Give the structural formula of 2-methylbut-2-ene. Analyse the given name: 2rmethylbut-2-ene methyl group main s C=C bond between, stchedt0C? cin Cand ¥ H-C-H Sabon ton a | wn I I Hence the stuctlfomulais HCC 6-6-1 i I Aoo4 (C) COMPOUNDS CONTAINING NON-HYDROCARBON SUBSTITUENTS, For nomenclature purposes only, nonhydrocarbon (i substituents fall into two classes, as tabulated below: not alkyl) Chass I substituents Indicated by prefix only: ‘Name Formula Prefix chloride =cl | chiloro- bromide Br bromo- iodide a iodo- ‘Note: Alkyl group (R) is also a prefix group. 292 Class 11 substituents Indicated by prefix or suffix: Name | Genera formula | Suffe Pref ‘Alkanoi acid a (carboxylic t acid) -C-0-H_ | -oleacia o 1 Ester -C-0- | ~oate rot Alkanoy! a chloride i sonsidered (acid chloride) c-a oy ehloride o Alkanal ? (cldehyde) -C-H -al Alkanot | (alcohol) -o-4 - When there is only one type of Class II substituent in a molecule, it is always designated by a suffix as shown in the table. In that case, it is referred to as a Principal Functional Group (P.F.G.). The usual IUPAC rules for naming still apply, with the following points to note: 1). The P.FG. has priority over carbon-carbon unsaturated centres (which are still named as suffix) and prefix groups. So the main carbon chain is selected to include the maximum number of P.F.G. and is numbered to give the smallest possible number to the P.F.G. 2) If the P.P.G. contains a carbon atom, then the carbon atom is also included in the main chain (e.g. the carbon atom of a —COOH group is part of the main chain). 3) In joining the main chain name and suffix name, the letter ‘eis cancelled off if followed by a vowel (ie. a, ¢, i, 0, u), even if there is a number between them. 293HH OW lees For example, H-C-C—C-Ht 8 propan 2-1 (not propane2-0l) ti H OHH cancelled off a vowel 4) In naming alkanoic acids, esters, alkanoyl chlorides or alkanals, no ‘umber is attached to the suffix name, as it is understood to be | ‘Thus CHsCH, COOH is named as propanoic acid (not propan-1-oic acid), and CH, CH, CH, CHO as butanal (not butan-1 al) (On the other hand, in naming alkanols containing 3 or more carbon ‘atoms in the main chain, a number must be attached to the suffix name. Thus CHOH is named as methanol, CH CH; OH as ethanol, but CHsCH, CH, OH as propan-I-ol (not propanol), and CH;CHCH, i as propan:2-ol (not propanol). bu A brief summary Priority (in choice of main chain and direction of numbering) Class Il substituents. carboncarbon prefix (@sPFG) unsaturated centres groups ‘Arrangement of various parts in the name Prefix | main chain| carbon-carbon | Class I substituents | groups | name | unsaturated centres] (as PF.G.) | suffixes Example 176 Formula 1UPAC mame x,CH, C(oHCH, 2-methylbutan-2-ol | Z yutane-2-0l by (ot 2ethylbutane2-cl) CHyeomewoneH, —_—_2-methy!butane2,3-do} \ ca, not Sinceled off because followed by d (not a vowel 294 CHCH,CH=CHCH,OH = pent-2-en-1-ol (rot pent-2-ene--al) x, €c1, 6H, CHO 3,3-dichlorobutanal (ot 33-dichlorobutanes!) ¢H,CH(CH, COC 2-methylpropanoy! chloride 2 separate words (not 2-methylpropaneoyl chloride) CH,CH(CH, COOH 2-methylpropanoic acid (not 2-methylpropangoie acid) Example 17.7 Write the structural formula of 2-methylpropanoic acid. Analyse the given name first: 2-methylpropat 7 et ° Zz améthyl main carbon group at chain contains tl C2 3 carbon atoms a—C—OH group at C-l Steps taken: 1) C-C-¢ write main chain only 2 CO 1 ‘number the main chain and attach ¢-¢-C-OH side chains 3) 4 H H-C-H O HOH add hydrogen atoms 295Naming of esters ‘The name of an ester contains two separate parts: ‘named as alkyl named as alkanoate The first part (alkyl) indicates the alcohol and the second (alkanoate) indicates the acid from which the ester is derived. For example, HO OR trot CH,COOCH, (H-¢-€-0-C-H) is called methyl ethanoate It isthe exter 1 H H of methanol and ethanoic acid. Example 17.8 Give the IUPAC name to CH,¢(CHs ),COOCHsCHs. ‘The name is ethyl 2,2-dimethylpropanoate, alcohol part acid part name FURTHER POINTS TO BE NOTED: 1) It is important to realize that most organic compounds are 3-dimen- sional and the orientation of their structural pictures on a sheet of paper does not affect their naming. For example, all the following structures are the same (2-methyl- pentane), although they seem to look different. CH,CH,CH,CHCH, CH 1 I CH; CHCH,CH, tot CH, CHs 296 CHS CHCHs I CH, i CH, CH; etc. 2) Naming of salts of alkanols and alkanoic acids Sodium salts of | Compounds | ‘he compounds Examples ROH RON CH,O-Na* sodium alkanol Sodium alko methoxide CH;CH;O'Nat sodium ethoxide CHCH;CH;0"Na* sodium propoxide (CHsCH, CH; CH; Na" sodium butoxide ° 0 ° ( t 1 sodium R-C-OH |R-C-ONs* | H-C-O'Ns —_methanoate alkanoic acid_| sodium alkanoate ° 1 sodium CHs-C-O'Ns" —ethanoate ° 1 sodium CH,CH,C—O"Na*_propanoate sodium (CH, CH, CH; C—O-Na* butanoate EXERCISE 17 1) Give the IUPAC names to the following compounds: @) ie CH,CHCH, © Ch 1 CH,CCH, I CH ) wae CH,CHCH,CHs @ CH CH, lot CH,CHCH, CHCH, 297© (CH, CHCHCH, CH i CH, CH @ CH,CH=CHCH, 0 Cs cxc=cridscn, wa dice, (CH cacnicnoH (0) OH I HOCH; CHCH, OH oe CH, CCH, COOH I CHy (8) (CH;CH, CH, COO), Mg, (v) CH; CH, CH, CHO (w) CHyCH,COOCH, CH (@) 23-dimethyibutane (©) 1-bromo-2-methylpropane 298 () CHsCH; CH=CH; (h) Cs CH,C=CH; oO a CHjCHCH, CH, Br @ On I CH,CHCH, CH (n) CHS \ CHSCCH, 1 oH ) CHS I CH;CHCOOH © Hs HOOC.CHCH; COOH o CH; 1 CH; CH, CHCH,COCL (¥) CH,COOCH, (&) CH3CH, CH, COOCH, CH, CH 2). Give the structural formulae of the following compounds: (b) 2,4-dimethylpent-2-ene @ 3-chlorobutane-| 2 HCI) _ Hie r/\e water, water 2 4 wat t=) 0 ® ro Hydrogen chloride dissolves The greater atmospheric When edge of funnel is inwater faster than itis prestre (P) pushes water exposed, the water sucked produced. The pressure up inside the funnel. The up falls back, and the cycle Inside the funnel (and as water level outside the is repeated. generat) bocomes lest Tunnel falls. than atmospheric USE OF PIPETTE AND BURETTE IN VOLUMETRIC WORK Pipette Before use, a pipette should be washed with water frst. Then it should be washed _— graduation with the solution it is to measure out. mark (This step cannot be omitted, otherwise the solution to be sucked in will be diluted with the water film on the inner wall of pipette.) To fill the pipette, dip the lower bulb stem of it well below the surface of the solution. (If tip of pipette is just below surface of solution, the solution is liable to be sucked into the mouth.) Suck solution tower up until the liquid level is about 2 cm above sem the graduation mark. Close the top end of the pipette with - the forefinger. Holding the pipette vertically, aa gently relax the pressure of the finger until the bottom of meniscus of the solution just touches the graduation ‘mark. Finally transfer the solution to a conical flask which has been prewashed with water. When all liquid has seemed to drain out, touch the inside wall of flask with the tip of pipette two or three times. After this, there will still be some residual liquid in the pipette, but you must not blow or shake this out because allowance has been made for this when the apparatus is calibrated. Mouth pipetting may be used (but with care) when the liquid to be transferred is a very dilute (concentration not greater than 0.1 M) solution of non-poisonous and non-corrosive substance (eg. 0.05 M NazC0s). In all other cases (especially for corrosive, poisonous, volatile or unknown liquids), a pipete filer must be used. A pipette filler Burette Before use, @ burette should be washed with water and then with the solution itis to deliver Fill the burette with the solution (a funnel may be used in doing this, but it must be removed from burette immediately after use). Clamp the burette vertically in a stand. Open the stopcock briefly to fill the part below it with the solution (there should not be any air bubbles). With your eye on the same level as the meniscus, take the initial burette reading, When performing a titration, the conical ask containing the aliquot is placed on a white tile under the burette so that the burette tip is inside ‘the mouth of the conical flask. The burette stopcock can be conveniently 309sanipulated with the thumb, ist and second finger of the left hand, with the right hand free to switl the conical flask continuously during titration ‘The solution is run out until the end point is reached. Close the stopcock and take down the final burette reading SAFETY IN LABORATORY Basic laboratory safety rules All students should observe the following rules: (1) Do not work in the laboratory without supervision of the teacher. 2) Do only the experiments assigned or approved by your teacher. Unauthorized experiments should never be attempted. (3) Report all accidents to your teacher at once. In case any chemicals get into your eyes or onto your skin, wash the affected area immediately with plenty of water, then report to your teacher. (4) Always prepare for an experiment by reading the experiment book (and corresponding references) before coming to the laboratory Follow the directions exactly, noting particularly all precautions. (5) Never run in the laboratory. Do not Jeave your bench unless it is necessary. (6) Do not take any object or chemical away from the laboratory without teacher's permission. (7) When you take a reagint bottle off the shelf, read its label carefully to make sure that the bottle contains the chemical you want. Put ‘the bottle in its original position immediately after use (8) Never return unused chemicals to the stock bottles. Do not put any dbject into a reagent bottle (except the dropper with which it may ‘be equipped). (9) When weighing, do not place chemicals directly on the balance pan (10) Alt spillages (on floor or bench) should be cleaned up at once, (AU)Hot objects must be placed on a heat-resistant surface (e.g. a ceramic mat), and not directly on the bench. (12)Wash the glasswares as soon as possible after using them, but let hot ‘ones cool first before washing. (13)Solid wastes (eg. used matches, broken glass, filter paper, copper turnings, etc.) should be disposed in the waste bin and never in the sink, Organic liquids and residues should be put in special waste-disposal containers (not in sink). 310 Safety precautions Fire and burns (1) Be familiar with the location and use of emergency equipments such as first aid materials, sand bucket, fire extinguisher, fire blanket an eye wash bottle. ’ — @) Never place a flammable liquid near naked flame. Heat flammable liquids only with water, steam or oil bath (@) Never throw lighted (or smouldering) paper or match into a waste bin. () When you have no immediate use of the Bunsen bumer, iurn it off or tum to a low luminous flame. If you leave it lighted with a non- luminous flame, you are likely to forget it and burn your sleeve. (5) A Bunsen burner which has ‘struck back” should not be picked up by naked hand as it has become very hot. (©) Be careful of buns caused by hot glass apparatus (hot glass looks very much like cold glass). Got dat oe (1) Take all necessary precautions to prevent spurting of hot liquids durin fas spurting iqui 8 (8) Never look down heated vessels (test tubes, flasks ete.) or point them at any person, (9) Wear safety goggles for eye protection in operations which are hazardous or potentially hazardous. Poisoning ‘Most chemicals kept in a laboratory are poisonous. (1) Never taste any chemical or solution in laboratory. (2) Do not inhale vapours of chemicals unnecessarily. If you have to find the odour of a gas, do so with great caution. Do not put the vessel containing reacting substances right under your nose. Just ‘fan’ a litle of the gi towards you by sweeping your hand oer the Lop of the vessel. (3) Use the fume cupboard for experiments involving poisonous gases. (4) Wash your hands before leaving the laboratory Danger from acids and alkalis Concentrated acids and alkalis are highly corrosive and extremely dangerous to the eyes. 31(1) Bxert great_care when handling concentrated acids and alkalis, especially when they are hot. (2) When you dilute concentrated sulphuric acid, always pour the acid (a little at a time) into a large quantity of water with constant stirring. Never pour water into concentrated acid, otherwise acid may spurt out Safety equipment Bye and face protection Students should wear protective spectacles or goggles in all circum- stances in which there is a potential danger to the eyes. Safety screen Safety screens made of transparent plastics should be securely fixed to protect both teachers and students when any experiment is demonstrated in which there is a possible danger of explosion or implosion. Fume cupboard ‘A fume cupboard should be used for experiments involving the ‘generation and handling of poisonous gases. Hazardous chemicals ‘A hazardous chemical is a substance which would be harmful to those who come into contact with it. Hazardous chemicals may be divided into five groups: 1. Flammable chemicals 2. Corrosive chemicals 3. Toxic chemicals 4, Unstable chemicals 5. Carcinogenic chemicals Flammable chemicals Flammable chemicals are substances that easily catch fire. These include some gases, volatile liquids and finely divided solids. Common examples are: carbon monoxide, hydrogen, methane; organic solvents 312 (eg. acetone, carbon disulphide, ethanol, methanol, ether, ethyl ethanoate ete); potassium, sodium, finely divided metals (such as aluminium, magnesium and zinc) and yellow phosphorus. Corrosive chemicals Corrosive chemicals are substances that destroy human tissues when in contact. Common examples are: concentrated mineral acids (hydro- chloric acid, sulphuric acid and nitric acid), concentrated ethanoic acid, concentrated ammonia solution (880 ammonia), sodium hydroxide, potassium hydroxide, hydrogen peroxide, silver nitrate, anhydrous aluminium chloride, phosphorus chlorides, potassium, sodium, phosphorus. and bromine. ‘Toxic chemicals Toxic chemicals are poisonous substances. They can be absorbed into the human body through skin, lungs or digestive tract. Common toxic chemicals are: halogens, hydrogen sulphide, carbon monoxide, nitrogen dioxide, sulphur dioxide; carbon disulphide, methanol; cyanides, mercury and its compounds, barium and its compounds, lead and its compounds, ‘chromium and ils compounds and oxalates. Unstable chemicals Unstable chemicals, in respect of storage, are those which may start reactions spontaneously upon sudden change in temperature, pressure or mechanical friction and shock. The reactions are usually explosively violent. Common examples are: yellow phosphorus, potassium, sodium, hydrogen peroxide, chlorates, ammonium nitrate and ammonium nitrite. Carcinogenie chemicals Carcinogen:e chemicals are substances that would cause cancer or are suspected to cause cancer. Examples are: asbestos, benzene, aromatic amines, chromates (particularly insoluble ones), tetrachloromethane and trichloromethare. Hazard warning symbols on reagent bottles ‘A hazard waming symbol gives warning of a hazard. There are five common hazard warning symbols: 313,1, Caution, risk of fire 2. Caution, risk of strong oxidizing agent 3. Caution, risk of explosion 44, Caution, toxic hazard 5. Caution, corrosive substance 1 2 3 Flammable Oniaiing Explosive 4 5 =) fe Toxic Comoxive Example 184 Which hazard warning symbol(s) should be put on bottles containing (a) sodium (stored under paraffin oil) (6) yellow phosphorus (stored under water) {c) 880 ammonia (concentrated ammonia solution) (d) iodine fe) bromine (9) mercury (g) concentrated nitric acid (h) concentrated sulphuric acid (i) potassium permanganate (j)_ carbon disulphide (k) oxalic acid (ethanedioic acid) (2) barium chloride (@) Sodium: flammable, explosive, corrosive (b) Yellow phosphorus: flammable, explosive, corrosive (©) 880 ammonia: corrosive (@) Iodine: corrosive, toxic 314 (6) Bromine: corrosive, oxidizing, toxic (9) Mercury: tex (@) Concentrated nit acid: oxidizing corosve (h) Concentrated sulphuric acid: oxidizing, corrosive (@ Potassium permanganate: oxidizing @)_ Carbon disulphide: flammable, toxic (k) Oxalie acid: toxie (®) Barium chloride: toxie Reagents which require special precautions Concentrated sulphuric acid Concentrated sulphuric acid is a strong oxidizing agent and a dehydrating agent. It is very corrosive. Dilution of the concentrated acid should be carried out by adding the acid slowly to water with constant stirring. (Never pour water to the acid, otherwise the acid would spurt out.) If a mixture containing concentrated sulphuric acid has to be heated, heat it very gently. Never mix the acid with solid potassium permanganate or with chlorates (otherwise explosion would occur). Potassium, sodiam and yellow phosphorus Potassium, sodium and yellow phosphorus must be used in very small {quantities and with due understanding of their properties. Yellow phosphorus burns skin and must be handled with tongs. Being very flammable, it is stored under water. (It smoulders in air.) Yellow phosphorus shculd be cut only with care under water in a large glass container. It can be blotted dry very gently with filter paper. The tongs/ filter paper should be heated/burnt after use to got rid of any adhering phosphorus. Iodine Solid iodine and its vapour will cause bun and stains on skin and clothing. Its vapour is poisonous and even small quantities would irritate ‘mucous membrane if inhaled. Sodium thiosulphate solution can remove iodine stains on skin and clothing.Silver nitrate Silver nitrate (Golid or solution) would react with skin and stain it black. Exercise care when working with silver nitrate, and avoid its spillage on skin and clothing. However, do not be alarmed when you discover some dark stains on your hands — these stains will wear away in a few days. EXERCISE 18 (1) Suggest five reasons why small quantities of chemicals should be used whenever possible. Fractional distillation ‘Adsorption ‘Chromatography Crystallization Decantation ‘Which method given above is best for performing the following? (@) Obtaining pure oxygen (bp. ~183°C) and pure nitrogen (b-p. =196°C) from liquid air. (©) Obtaining a clear saturated solution from dense, undissolved solute. @) moom> (©) Removing the coloured matter from a solution of tea. (@ Separating the various pigments in the green colouring matter of ass. (©) Obtaining copper(II) sulphate crystals from its aqueous solution. (O Separating a certain male hormone from an extract of rat's tests, @) The apparatus partly shown ligud with boiling - point higher than in the following figure was ad used by a pupil to find the melting point of a solid. State three errors that he hhad made in setting up the apparatus, melting point tube 1 thermometer 316 (4) A pupil was given an unknown white solid X to identify, He found its melting point to be 133°C. He looked up a chemistry data book and found that a compound called urea had & melting point of 133°C. To find whether X is really urea, he mixed some pure urea and X together. The melting point of this mixture was determined to be 129°C. What can he deduce about solid X from this? Xisurea Xi impure urea Xisnot urea Xmay de urea X must not be a pure compound moowD> (5) Name the proper chemical apparatus or instrument which would be ‘used in each of the following: (@) To contain a solid which is to be heated very strongly (b) To store a small amount of solid temporarily (©) To collect and measure volume of a gas (@) To transfer small amounts ofa solid (©) To grind a solid into fine powder (f) Tostir a mixture (g) Toadd drop quantities ofa liquid (h) To separate immiscible liquids (without involving heating) (To mix solutions for observing any changes (To contain a solution which isto be evaporated to dryness (&) To hold a test tube for heating (To pick up a hot evaporating dish (mm) To generate a gas whenever required (n) To deliver a certain fixed volume of liquid (0) To deliver a variable volume of liquid (p) To measure volume of a liquid (@) Todry (or to keep dry)a solid () Tomeasure the mass of an object with an accuracy up to 0.1 g (8) To measure the mass of an object with an accuracy up to 0.0001 g (®) To follow the change in mass of a reaction vessel and its contents in the course of a reaction (u) To support a crucible on tripod (W) To fix an apparatus securely in place (w) To hold a small amount of sample for buming in a gas jar (x) To filter @ suspension () To provide a heat-resistant surface for placing hot objects (@) To condense the vapour of a volatile liquid during its preparation 317© a 318 (@) Volume of liquid in a test tube can be roughly estimated from the depth of liquid, Given that a 150 X 16 mm test tube has a cross- sectional area of about 1.5 cm?, to what depth should the tube be filled if the volume of liquid to be added is (i) 3 em? (ii) 5 em? (ii) 9 cm? (iv) 20 cm? (b) The following is an extract from a laboratory manual: ‘Add about 3 cm? of 0.06 M sodium sulphite solution to about 3 om? of an acidified solution of 0.02 M potassium permanganate solution in atest tube.” ‘A student performed the experiment but did not follow the instructions exactly. He added about 1 cm? of the sodium sulphite solution to about 10 cm? of the acidified potassium permanganate solution. Comment on results of his experiment when compared with the standard one. (©) The following is an extract from a laboratory manual: ‘Add about 2 em? of acidified solution of 0.1 M silver nitrate solution to about 2 em® of 0.2 M sodium chloride solution in a test tube, Observe what happens. Add excess 2_M_ ammonia solution to the above mixture. Stir with a glass rod, Note what happens.” ‘A student doing the experiment carelessly added about 7 cm depth of the acidified silver nitrate solution to about 7 em depth of the acidified silver nitrate solution to about 7 em depth of the sodium chloride solution in a 150 X 16 mm test tube. He added the ammonia solution up to nearly the brim of the tube ‘and then stirred the mixture with a glase rod. Compare the results ‘of his experiment with the standard one During an experiment, a student at fist used a medium nonuminous Bunsen flame, with the gas supply and airhole both at helf-open positions. In order to get a hotter flame, he turned the a-hole fully ‘open without adjusting the gas supply. At once, he observed the flame to ‘strike back’ with a hissing sound. After a minute, he tumed off the gas supply and then attempted to close the airhole by tuning the collar with bare hand. He was unfortunate to burn his fingers in doing so. @ What was the cause of the ‘striking back’ of flame? (©) What should he do to get a hotter flame? (©) Why did the student burn his fingers? (@ What should he do in order to light the burner again? (8) While a student was heating a liquid in a test tube to a temperature very near to the boiling point of the liquid, he suddenly discovered that he had forgotten to add ant-bumping granules to promote smooth boiling of the liquid. Should he add anti-bumping granules to the hot liquid at this moment? (©) Two set-ups I and I are shown below: a mixture of ethanol, ‘cthanoie acid and Tew drops of cone. #80. held by test tube holder in this position heat with roaring Name Setup! stopper Liebig condenser clamp pear-shaped Mask mixture of ethanol, ethanoic acid nda few drops of cone. HO. antibumping gancle Setup 319(@) Point out the mistakes in setup I. (©) Point out the mistakes in set-up II. (©) Supposing all the mistakes in set-up I and Il are properly corrected, which of them is more suitable to obtain a high yield of the product ethyl ethanoate? (10)Two possible methods of collecting chlorine gas are downward delivery (upward displacement of air) and displacement of water. (@) What property of chlorine gas enables it to be collected by (i downward delivery (ji) displacement of water? (b) List the advantages and disadvantages of collecting a gas by displacement of air (upward delivery or downward delivery). (©) List the advantages and disedvantages of collecting a gas by displacement of water. (@ A good way of collecting gases is to use a gas syringe. What are ‘the advantages of this method? Put down any disadvantages also. the help (© Given a gas syringe full of wet chlorine, explain, of a diagram, how you would dry the gas. (©) Suggest methods to collect the following gases: (dy carbon dioxide (il) hydrogen (iil) pure dry oxygen (iv) sulphur dioxide () pure ammonia (vi) nitrogen dioxide (vil) hydrogen chloride (11)Lead(l) nitrate decomposes on heating as shown by the following 320 equation: 2Pb(NOs)a(6) — 2PO0() + 4N03(8)+ 0:68) Draw one or mote labelled diagrams to show how you would prepare a sample of nitrogen dioxide as free from oxygen. You are given the following apparatus and material: hhard-gass test tube fitted with stopper carying 2 glass tubing, Bunsen burner, wire gauze, tipod, box of matches, stand, boss and clamp, Utube fitted with stoppers carrying delivery tubes, rubber tubings, spring clip, large beaker, gas syringe, tap water, freezing mixture, lexd(l) nitrate crystals; access to fue cupboard (12) he following set-up was used in an experiment to prepare and collect chlorine gas. concentrated hydrochloric acid rmanganese(1V) oxide concentrated sulphuric acid (@) Write an equation to represent the reaction between concentrated hydrochloric acid and manganese(IV) oxide. (b) What is objectionable concerning the above set-up? (©) At the end of the experiment, the delivery tube must be removed above the water surface before heating is stopped. Why? (@) How would you modify the above set-up to prepare pure, dry chlorine? (13)A student added a small piece of sodium metal (about the size of rice grain) to @ few cm® of industrial alcohol (containing about 95% ethanol and about 5% water) in a wet test tube. He observed that 1 colourless, odourless gas was given out and it was shown to be hydrogen by the ‘pop’ sound test. He thereby concluded that sodium reacts with ethanol to form hydrogen gas. Was his conclusion valid? Why? How would you carry out the experiment? 321(14)A student used the following setup to prepate sulphur dioxide. thistle fannet copper # sulphuric sulphur acid dioxide concentrated sulphuric acid Point out the mistakes he had made in the set-up. (15) The following passage describes the preparation of a sample of copper(II) sulphate-Savater, CuSO, .5H,O. Read the passage carefully and then answer the questions following, “Half fill a beaker with bench dilute sulphuric acid and add copper(II) carbonate powder. Stir continuously, adding more copper(II) carbonate until some of the solid remains undissolved. Warm gently for about fen minutes and then filter the suspension. Place the filtrate in an evaporating dish which is heated by a steam bath. Dip a glass tubing into the filtrate at intervals. Take out the tubing and observe for formation of any small crystals on cooling. When this happens, remove the heating source and allow the solution in the evaporating dish to ‘cool. Filter off the blue crystals formed, wash them two or three times with a small quantity of cold distilled water and then press the crystals between filter papers.” (@) What is the approximate molarity of bench dilute sulphuric acid? (©) What would be observed when copper(II) carbonate is added to the dilute sulphuric acid? Write an equation to represent the reaction that takes place. (©) Why is excess copper(II) carbonate used? 322 (a) Why is the filtrate heated? Why should a steam bath be used? (e) What is the purpose of ‘testing’ the solution with glass tubing? (Explain why the crystals should be washed. Why should a small {quantity of cold distilled water be used for washing? (g) Why are the crystals pressed between filter papers? (16)A student was given a standard solution of hydrochloric acid (1.012 M) and an approximately 1 M sodium hydroxide solution. He was asked to find the accurate concentration of the sodium hydroxide solution by titration. He performed the experiment, describing his method as follows: “A burette was washed with water and then the sodium hydroxide solution provided. The burette was clamped vertically in a stand and then filled with the alkali solution by pouring the solution above eye level into a funnel (which was allowed to stay on top of burette ‘throughout the titration). A 25.0 cm? pipette was washed with water and then the standard hydrochloric acid. The acid was sucked by mouth into the pipette to above the graduation mark. The liquid level in pipette was then adjusted to the mark, The acid in pipette was delivered into a conical flask which had been prewashed with water and then the acid, When all the acid in pipette had seemed to drain ‘out, the residual liquid at the tip of pipette was blown out. 2 drops of litmus solution were added to the acid solution. The intial burette teading was taken and then the alkali solution was run into the acid ‘until the indicator changed to its ‘neutral’ purple colour. The final burette reading was noted.” Point out any mistakes he had made in his titration. (17) Explain the following: (@) Glass stopper should not be used for bottles containing sodium hydroxide solution. (©) A bottle of tetrachloromethane is usually kept in fume cupboard. (©) Hot solution should not be poured into a volumetric flask (18)What type of experiments must be carried out in a fume cupboard? (9)Which of the following reagents are usually stored in a brown bottle? Why? (a) Concentrated sulphuric acid 323(b) Concentrated nitric acid (©) Concentrated hydrochloric acid (@) Sodium hydroxide solution (e) Hydrogen peroxide solution (D) Silver nitrate solution (g) Bromine water (h) Tetrachloromethane (20)Which of the following solutions can stain skin black or brown? (a) Silver nitrate solution (©) Lead(It) nitrate solution (©) Barium chloride solution (@) Iodine dissolved in ethanol (¢) Sodium hydroxide solution (0) Hydrogen peroxide solution (g) Concentrated sulphuric acid (21)Which of the following substances should never be allowed to contact with skin? Give reasons. @) Yellow phosphorus () Calcium hydroxide (©) Potassium hydroxide (@) Magnesium chloride (@) Anhydrous aluminium chloride (O) Magnesium powder @) Potasium (h) Sodium cyanide (i) Mercury @) Barium nitrate (k) Barium sulphate (®) Sulphur (a) Concentrated sulphurie acid (22)Which of the following procedures are highly dangerous and should ‘note attempted? (@) Heating solid ammonium nitrate or ammonium nitrite, (b) Adding concentrated sulphuric acid to solid potassium per- ‘manganate, (©) Pouring water onto concentrated sulphuric acid 328 (@) Heating a mixture of magnesium powder (or zinc powder) with sulphur, © Ieniting a hydrogen — air mixture from a gas generator. (© Grinding and then warming a mixture of potassium chlorate ‘with carbon and sulphur. (2) Dropping a large stick of yellow phosphorus to water. (2) Dropping a large piece of sodium to water. (@. Evaporating a solution of sulphur in carbon disulphide in a fume cupboard at room temperature. (23)A student was performing an experiment on combustion of sodium in chlorine: He cut out a rather large piece of sodium metal and placed this in a deflagrating spoon. He ignited the sodium with a Bunsen flame and plunged it into a gas jar of chlorine. He observed that the sodium continued to bum with a golden yellow flame, with formation of a lot of white fumes. When the reaction seemed to subside, he took fout the deflageating spoon and washed this under the tap. To his alarm, an explosion occurred. What was the cause of the explosion? What is the proper way of doing this experiment? (24)A student investigated the action of concentrated sulphuric acid on ‘copper metal. He placed a spatula measure of copper turnings in 150 X 16 mm test tube. He then added about 10 cm? of concentrated sulphuric acid to the tube. He heated the mixture with a roaring Bunsen flame with constant swirling of the tube. After the gas evolved was tested, he washed the hot tube (with its contents) under the tap. Point out the mistakes the student had made in his experiment. 325(25) An experiment was carried out to demonstrate the burning of hydrogen gas to form water, by using the set-up shown below: SS ieee 3 See eccrine Y ‘water vapour) Ne wateh lass (o collect any water formed on the underside cof beaker) “anhydrous caleium ine dilute Chloride franale sulphuric acid ‘A burning splint was applied to the end of delivery tube at A in an ‘attempt to ignite the hydrogen gas coming out. What do you think would happen? What precautions should be taken to perform the experiment safely? (26)State, with reasons, whether the suggested immediate treatment is appropriate in each of the following cases: (if not, suggest an appropriate one.) (@ Wash skin splashed with concentrated sulphuric acid with dilute sodium hydroxide solution (2 M) and then with a lot of water. (©) Breathe in ammonia gas from dilute ammonia solution (2 M) to alleviate poisoning by chlorine gas. (© Wash skin burn caused by bromine with sodium sulphate solution. (@ Wash eyes splashed with sodium hydroxide solution with dilute cethanoie acid, and then a lot of water. 326 QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS FINDING MOLECULAR STRUCTURE OF AN ORGANIC ‘COMPOUND In a school laboratory, the structure of a simple unknown organic ‘compound can often be found by following the scheme below: ‘unknown organic ‘compound quantitativeanalysis gas density study of chemical {ofind composition determination _properties by mass empirical ‘molecular formula mass uM [retecrar Lak Fimational mula pom) I structural formula See p. 328. 327Usually, after the molecular formula of an organic compound has tbeen found, the functional group(s)* present should be found also before the molecular structure can be determined (except when the compounds are so simple that only one single structure is possible for a molecular formula, eg. CH,, CzHa, CH,OH ete.). The functional group(s) present in a compound may be identified by performing chemical tests on the compound. DETERMINATION OF EMPIRICAL AND MOLECULAR FORMULAE ‘A detailed account on this was given in Chapter 6. CONCEPT OF DOUBLE BOND EQUIVALENT (D.B.E.) ‘After finding the molecular formula of a compound, much informa- tion about its identity will be obtained if its degree of unsaturation can be found. This is done by calculating a number called Double Bond Equivalent (D.B.E,) from its molecular formula, as shown below: DBE. of an ans a ‘compound = 2% #0-0fC atoms 2— (0. of no. of X atoms) (openchained) (X= halogen) Note that in the above formula, the number of oxygen atoms is not involved. When D.BE. = 0, the compound is saturated. = 1, the compound has 1 double bond. 2, the compound has 2 double bonds or I triple bond. (ote: 2 double bonds are equivalent to | triple bond in this concept.) Example 19.1 Find the degree of unsaturation of compounds with the following ‘molecular formulae: (2) CiaH3e (b) Cable (c) Cells (4) CzHsCl (e) CaHi00 (f) CHa. (You may assume that all compounds are open- chained) * A functional group is an atom or group of stoms responsible for most of the chemical propeties of a compound 328, = 2K12+2-26 (@ ForCyBss, DBE. : ° ie. itis saturated. (©) For CaHs, ppg. = 2%402-8 24 ie. ithas 1 double bond, (© Forse, DBE. = 24542=8 sp ie. ithas 2 double bonds or 1 triple bond @ ForcHcl, DBE. = 2X22 ° ie. it is saturated, (© ForCeHy0, DBE. = 2X442=10 ie it is saturated. (© ForCaHy0,, DBE. = 24422 -8 = | ie. ithas 1 double bond. Example 19.2 Give the names and structural formulae of two isomers which belong to the same homologous series and which have the molecular formula C3Hy0. (HKCEE) easing (st requted in the anova, but Incidd et for reader's eferen) DBE. otcompound = 2372-8. 0 Since the compound is saturated, the oxygen contained must be present as “OH of R-O-R’ (ether linkage), but not a8 C=O double bond (in alkanal cor alkanone) HHH HH H 1 ete Possible isomers are: H-C—C-C-OH, H-C-C—C-H Pi it HHH H OHH propan-1-ol propan-20l Note: CHsOCH;CH, will be a third isomer, but this belongs to another homologous series* — the ether series. +A homologous series is» series of organic compounds having similar structures and an be represented by the same general formula, eg. all members in the alkane series can be represented by the general formula Cyan. 329‘The concept of DBE. has another application: to find whether a given, molecular formula corresponds to a possible compound or not. The argument is that values of DBE. can only be zero or positive integers, but never fractions or negative numbers. Example 19.3 Predict which of the following molecular formulae do not correspond 10 a possible compound: (a) CHO (b) CsHly (¢) Calls0 (A) CyHy002 2X2+2-6 (@) For C,H.03, DBE. z 0 (b) ForCsHy, ppe.= 2%5 25 © Forco, pe.= 2X442=9 = 95 2x3 @ ForCsHy0:, DBE. It is obvious from above that the molecular formulae in (b), (c) and (4) cannot correspond to possible compounds. STUDY OF CHEMICAL BEHAVIOUR TO FIND FUNC- TIONAL GROUPS PRESENT IN COMPOUNDS ‘As explained before, mere knowledge of molecular formula and D.B.E. value of a compound may not be sufficient to enable us to deduce its molecular structure. Very often, the functional group(s) present should also be found by a study of its chemical behaviour. In the following account, common reactions of some homologous series are summarized. (A) ALKANES (paraffins) Alkanes are saturated open-chained hydrocarbons with general formula CyHane2 (or RH). Being saturated, they are rather chemically inert. They do not react with acids, alkalis, dehydrating agents, reducing agents or oxidizing agents under usual conditions. 330 Reaction type, reagents and conditions ‘Products’ Observations tower alkanes combustion, exe Ons ianite 9, gy,q Cer aman sooty fame because of low carbon/hydrogen ratio 250° 400°C substitution, Xz, or diffuse ee eee amixture of discharge of the haloalkanes yellowish green +HX colour of Cl, or red colour of Bra (vuch faster in direct sunlight) sunlight Alkanes (7 ectivity of Xy! Ch > Bra) cracking Se lower (yrolyss) ——withor without + alkenes catalysts Note: Substitution reaction is a reaction in which an atom or group of atoms is replaced by another atom or group. Cracking is the breakdown of large hydrocarbon molecules into smaller ones by application of heat and/or addition of catalysts. (B) ALKENES (olefins) Alkenes are unsaturated open-chained hydrocarbons with general formula CqHgq. With a carbon-carbon double bond, they are quite reactive chemically and the chief reactions are addition reactions (cf. substitution reactions for alkanes) 331REACTIONS OF ALKENES (©) ALKANOLS (alcohols) ‘They are compounds with the general formula CyH2q4+10H (or simply, ‘Rector ype regensencondions —Pofuct Obert ROH). anh eu te ostomy tne It is important to distinguish between the following types of aleohols, == Eee ae as their oxidation products are different: amen ain, =f H H pe Ah 1 1 hee este R-C-OH = R-C-R’ smomma. . -¢-¢ ate er i 1 GsrCntnhy et corto tie oe Li i ay gat) state been oe) - ‘Coon (R= Hor alkyl group) (R,R’, R"= alkyl groups) ol — primary (1°) secondary (2°) tertiary (3°) alcohols eee x ow SB aor he a slen wt ay a AA primary alcohol is characterized by a —CH,OH group, a secondary alcohol by @ >CHOH group and a tertiary alcohol by a SCH group. ~ 8 OTe Example 19.4 ‘ Classify the following alcohols into 1°, 2° or 3 alcohols: sap nope ste (a) methanol (b) ethanol (c) propan-t-ol (d) propan-2-o1 a Sear {e) butan2-01 (f) 2-methylpropan-I-ol (g) 2-methylpropan:20l Ta eb The structural formulae ofthe alcohols are shown below: root us wo ; a ~g-E- the pple Kn, ecole lie i qe i oon (@) H4-C—on! (ot) H—C-+4+-C—on! (cies bad) rt | Vil t Hee win} ation __soxreoonm oo) \tinion steno waar | 6 Ge 2 tierh 1° alcohol 1 alcohol + Addition reaction is reaction in which two or more molecules react to form a single product. To distinguish between alkanes and alkenes by these reagents, do the test in shade (ot in ditect sunlight). Incase of alkenes, there will be rapid (almost instantancous) ecolourization of the halogens, while for alkanes, decolourization is very slow. Et 333uznp spunodwo> apron Jo s¥0) 119 ay et manos ne ot np su ayn ouap pow so Sty ce pono ee eur ce ena yd pmems a 1s panos dd, fa wate a9 ot uaous pao se winpe snqo> sey Ssooewen a ing dios a9 Jo weep 30} B96 “S295 sone ofnen-p9- ry spo equa capi | oxemoons (Dis "Woda sper svompuce pun sunt ad woos STONVYIV 4O SNOLLVaY zoos 3 =-o-m = 7 I = S = l z-o-= = po 1 Ra E en FF zouoe 3 (S-o} c= § z-o-n % moon Bo & | 1 z = 335, 334(D) ALKANOIC ACIDS (carboxylic acids) They are compounds with the general formula CyH2n+) COOH. or simply, RCOOH az ace Exee = Bs Bao 8232 > 3 gis SEES Sz 23 a2: Ese fe Bes Bie sist zy 2 $23 332 2295 33 2 gi gig Bac 22 f G2f FF! Bese 2a. g 336 S32 282% b3% S B85 852 S282 Bab 7 5 Be 2 a s Ess a = ° S + BS S £2 £26 die ¢ 6 Bi fi f, 282 F S82 98 22 53 fEe z 24 33 85 8 gs B82 i 3 2s OC8 CZs Sze gé y & SE ge zak “i & 3 : 5 3 > |g . 63 le |e eae IS 2 Z| 2 3s . 23 ge le 42 See 32 se ae & § de de 23 alg a £ Ee ae 32 ‘ Bs 4 3| g &ls & x gl |" 5 g 3 g & y 3 ql 336 Special behaviour of methanoic acid (HCOOH) In general, methanoic acid has chemical properties similar to those of other alkanoic acids (e.. it forms salts and esters). However, methanoic acid also has other properties which cause it to be markedly different from ethanoic acid and other members of the alkanoic acid series, as shown below: (1) Reaction with phosphorus{ V) chloride HCOOH(®) + PCI; (s) —> POC (6) + 2HCIG@) + CO) (Cf. CHs COOH(®) + PCI, (s) —+ POCIs(s) + HC\) + CH COCI®) (2) Dehyration BA (0) $22 HS. H.0(8) + COL) a (can burn with a blue flame) He No other alkanoic acid can be dehydrated in this way. (3) Reducing properties Unlike other alkanoic acids, methanoic acid does not contain an alkyl group R, as indicated in the following formuli R \c-0 0% ‘methanoic acid an alkanal other alkanoic acids (reducing agent) (reducing agent) (non-reducing agents) This special feature, namely, the absence of an alkyl group and the presence of a ~CHO group, probably explains why methanoic acid is 4 reducing agent while the other acids are not. ‘The reducing properties of methanoic acid are illustrated by the following reactions: (i) Silver-mirror reaction Tollens' Reagent HCOOH() FapQH)s]* heat” A8)* other products as silver, 337(Reduction of Fehing’s solution HcooH(g) Fehling’ solution (blue). cy, O45) + other products heat (ed ppt) (ii) Decolorizaton of acidified potassium permanganate solution KMn0./H HCOOH) SMROSE, si*(aq) + 1,01) + C0218) ‘The purple permanganate solution is decolourized. SUMMARY OF SOME IMPORTANT OBSERVATIONS AND CORRESPONDING INFERENCES Observation Inference 1. An organic compound that ‘compound is saturated burns with a non-sooty flame; ‘an organic compound that burns | compound is probably with a sooty flame unsaturated 2. Asteamy gas which fumes the gas is HCI profusely with ammonia 3. Acompound that gives HClon | presence of —OH group in the addition of PCL, compound (which may be ROH, RCOOH or H,0) 4. An organic compound that | presence of carbon-carbon decolourizes red Br; /CCl, mltiple bond (uicky even inthe dark or | (ie. purple KMnO,/E" solution in| or —C=C— bond) the cold 5. A.gas which gives the ‘pop the gas is Hy sound’ test 6. Acompound that gives Ha gas | the compound has acidic ‘when electropositive metals hydrogen; may be RCOOH, are added ROH, H,0 ete. 7. & gas which turns ime water | the gas is COs milky 8. A compound that liberates CO; | presence of -COOH group or When Na;C03 or NaHCO, is | mineral acid added 338 9. n 12. 13. ‘A compound that can decolourize purple KMnO./H" solution and turn K3 Cr, 07/H* solution from orange to green ‘A compound that gives silver niror with Tollens’ Reagent or sive a red precipitate with Fehiing’s solution ‘A compound having a pleasant, sweet fruity smell ‘A compound that gives en ester with alkanoic acid ‘A compound that give an ester with aleohol ‘An alkanol that can be oxidized to form alkanal and then alkanoic acid the compound is a good reducing agent (eg. alkanal or ‘methanoic acid) it isan ester presence of —OH group (in alcohol) presence of COOH group (or =COC ete) it is a primary alcohol (Le. it contains ~CH, OH group) 339A. CHART SHOWING INTERCONVERSION OF SOME ORGANIC COMPOUNDS fraction ‘itilaton Xa, UV ight bation) aa 1, caatng ig, Nas eat ota coal CGeornton) ie, 2 Ste 2 HX (aon) excess cone HyS0u.d o. Slab » Steir ays, ES Dae extgdeton ‘iigl hydro | veto) ety (oe Ps. X= BH) ae oes ne 50, “Sa, 3 a cove 11504, nei, a S (etn) aaeseaat | roy ™acoey | [NaOH (ot Nag6Os of NAHCOs) (Coo!) e cular case of 1° aloohols, For 2° and 3° alcohol, the *We conser nee the pst and alkanote acids oxidation products will not 340 Example 19.5 ‘Study the following list of compounds and answer the questions ‘that follow. (Give your reasoning in each case.) A CHsCH;CH,CHy B CH;CH=CHCH, C CHsCHh,CHh,CHyCH;0H —-D- CHsCH,COOK* E CHCH,COOH F o c1t,0-€-(Ctt, ety ° I CHO-C-(CH, )yCH ° I (CH,O-C- (CH CH G CHs(CH; hgCOO-Na* H_ CHsCH; CH; CH; CH,0°Na* (a) Which compounds are soluble in water? (6) Which compounds can conduct electricity in aqueous solution? (¢) Which compound would react most readily with bromine in tetrachloro- ‘methane? (d) Which compound would polymerize under high temperature and pressure? (e) How would you carry out the following conversions: (i) CoH (ii) EtoD? Write an equation in each case. (1) Which compound is a good detergent? Is it soapy or soapless? (8) How would you prepare the detergent mentioned in (f) from one of the compounds in the list? Write an equation for the reaction that ‘occurs. What is the process called? (@) D,E,G and H are soluble in water. D, G and H ate ionic compounds. ‘A molecular organic compound will be soluble in water if i stisties ‘wo conditions: (1) The compound has at least one functional group 341te. on, coo, --0-) ant a om ye boning it co nang hyo etal re poy ce mre Only compound E satisfies these conditions. (b) D.E,G and. D,G and H are ionic compounds E is a weak acid which ionizes slightly in water. (©) B. Although both A and B can react with bromine in tetrachloro- methane, B being unsaturated, reacts more readily under ordinary conditions. (@ B. Itis unsaturated and can undergo addition polymerization (© (Add sodium metal (not sodium hy éroxide) to C. ‘2CH, CH, CH2CH;CH,0H +2Na + 2CH,CH,CH2CHs CH; 0°Ns* + Ha (i) Add aqueous potassium hydroxide (or potassium carbonate) (oF. CH,CH, COOH + KOH — CH CH; COOK’ + H,0 (©) G. Atypical detergent molecule consists of 2 parts: (1) A hydrophilic (water-loving) group. (2) Along hydrophobic (water-hating) hydrocarbon chain. [A detergent molecule should have 8 to 18 carbon atoms, hence G (but not D and H) should be a good detergent. G should be 2 soapy detergent because the hydrophilic group is © COO". (Note: The hydrophilic group of soapless detergents is usualy =0805" or -S03") 342 (@) By alkaline hydrolysis of F which isa fat ° I CH,0—C—(CH,),4CHs | ° i CHO-C—(CH;);¢CH3(®) + 3NaOH(aq) | ° a i 0-C-(CH,)igCHy CHOW (a triester) 1 CHONG) + 3CH (CH )6COON9) CH, OH (@ soap) ‘This process is called saponification (i.e. soap-making).. Example 19.6 An experiment is carried out as ilustrated below: cotton woo! soaked with compound P pumice stone _L mo strong heat Gas Q is a hydrocarbon with a density of 1.75 g dm 6 75g dm at roo conditions It can decolourize a solution of bromine in tetrachloromethane and also acidified potassium permanganate solution. (a) Calculate the molecular mass of Q. 343(b) Deduce the identity of Q. {[c) Deduce the identity of P. (d) What is the function of the heated pumice stone in the experiment? (e) Predict, with reasoning, the product expected when Q reacts with hydrogen chloride, (@) Since molar volume of a gas at room conditions = 24 dm® :, molar mast of Q= 1.75 X 24= 42 Molecular mass of Q= 42 (b) Q can decolourize Br,/CCly and KMnO,/H"(aq), and is therefore an unsaturated hydrocarbon. Since Q has a molecular mass of 42, it should be propene CHyCH=CH, . (©) Since propene is obtained by passing vapour of P over heated pumice stone, P should be a Cs alcohol — either propan-1-ol CH CH, CH OH or propan-2-0 CH CHCH, oH (@) To provide a hot catalytic surface for dehydration of alcohol to occur. (©) 2 different addition products are possible: _ 70x, CH1, Cl (I-chloropropane) CH,CH=CH; + HOC CHsCHCH, — (2 (CHyCHsCOO), Mg + Ha (© CH,CH,COOH + cH,CH,CH,0H 2 crc, cooc cH. cH +H (@) CHsCHi,CH, OH + #50, —> CHsCH,CH,0S03H+ 0 CHyCH,CH,0SO,H = —> CHyCH=CH +H,S04 (e) CH,CH,CH,OH +PCl, © —> CH;CH; CH; Cl + POCI, + HCl CH,CH,COOH+PCk = —* CHaCH,00C1+POCI + HCL From the observations in (¢), the conclusion is that an OH group is present in both P and Q because — OH group reacts with PCls to give HCL ‘ga8 which fumes in moist air Example 19.8 When 6.9 ¢ of an inflammable organic compound X were burnt in ‘excess oxygen, 13.2 g of carbon dioxide and 8.1 g of water were obtained 4s the only products. From this calculate the empirical formula of X. Compound X reacts with PCI, to give a colourless steamy gas G which ‘fumes profusely with ammonia, On prolonged boiling with chromic acid, XX gives a substance Y which also reacts with phosphorus pentachloride 10 give the same colourless, steamy gas G. When X is heated with con- ccentrated sulphuric acid to 170°C or a little above this temperature, a colourless gas Z is produced, Z decolourizes bromine water but has no reaction with ammoniacal copper(I) chloride. Z has a vapour density of 14. Name, giving structural formulae where appropriate, the substances G,X, ¥ and Z and write equations for all reactions involved. (HKCEE) 346 ‘After combustion, the C and H in compound X are converted to CO: and HO respectively. 12 ‘ Mass of Cin CO; = 132x 32 = 3.68 44 vs fin tk0 = 81% 2, = 098 ‘Since compound X has a mass of 69 g and the only combustion products are CO; and H,O, the remaining mass must be due to oxygen present in X, Mass of oxygen in ¥ = 69-36 ~09 = 24g c H oO Relative mass ing) | 3.6 09 24 Relative no. of moles : (divide by atomic mass) 36 09 24 $$. 930 | 92-09 | 2#= 015 (aivide by the sate | 0.30 09 ous 20) o1s=? | o1s~® | oas~! ‘The empirical formula of X is Cz HO. Reasoning (ot roquited in the answer, but included here for readers’ reference) Information Inference Pals, colores steamy | Gi Hc1 and wo X shoul have aga | gay te cat dense fumes x stromie acid , PCY x Stromal y7ES.G | since ¥ gives HCI it should also contain “OH group (in alcohol or alkanoic acid) Because X can be oxidized to Y, X should be 441° alcohol, while ¥ is analkanoic acd. Z isthe dehydration product ofthe alcohol ‘X,s0it an alkene Let Z be (CH)qi (12+ 1X 2)n= 28 asd Zs CH = CH; (ethene) So X should be CHjCH;OH (ethanol), one. H»SO4 , colourless 110%” easZ Zhas vapour density of 14 ( x | 347Names and structural formulae are G: hydrogen chloride H—Cl HH 11 Xsethanol H-C-C-O-H Ys ethanoic acid ie HH HH HO i H Wt Z:ethene H-C=C-H I Equations for the reactions: C:H,0H +30;—+ 2CO; + 3H;0 CoHsOH + PCl,—+ C3HsCl + POC; + HCL HC1+NHy—> NHgCL canon EL, cHyc-H ° to} ° i H-C-C-0-H AOL, cu, ° ° I C-0H crC-on + Pa, — crie-ci+ POC, + C1 C,H,OH + H;S0,— CH, 0S0,H + H,0 C,H,0S0,H— CH, =CH, + H2S0, Br, +H,0— BrOH + HBr HH tt CH, =CH, + OH —> H-C-C-H 348 ri Br OH Example 19.9 There are four unlabelled bottles each containing a pure colourless organic liquid. The four liguids are propy! ethanoate, 3-methylpent-2-ene, 3echlorobutanoic acid and pentan-2-01. (a) Write the structural formulae of the four compounds, (b) Describe briefly how you could identify the unknown liquids using simple chemical tests, @ 0 cH, i I (CH3C-OCH, CH, CH CH,CH=CCH; CH propyl ethanoate 3-methylpent-2-ene a OH i I CH;CHCH, COOH CH; CHCH; CH; CH 3.chlorobutanoic acid pentan-2-ol (b) (1) Add Br2/CCl, to each of the liquids — only 3-methylpent-2-ene decolourizes the red bromine quickly. (2) Add sodium carbonate solution to each of the three remaining ‘unknown liquids — only 3chlorobutanoic acid effervesces, a colourless gas (CO; ) being produced. (G) Add sodium metal to each of the two remaining unknown liquids = only pentan-2-ol gives a colourless gas (Hl). Example 19.10 Describe a chemical method you would use in laboratory to separate «a mixture of L-chlorohexane and hex-3-ene into pure compounds. ‘Shake the liquid mixture with concentrated sulphuric acid at room temperature. Hex-3-ene, being unsaturated, reacts with concentrated sulphuric acid (by addition) and dissolves in it; I-chlorchexane has no reaction and remains as a separate layer. Separate the two liquid layers by a separating funnel. Hex-3.ene can be regenerated by heating (with care) the concentrated sulphuric acid layer. CH CH, CHCH, CH, CH, (0) M4 CH,CH,CH=CHCH, CH (g) 1 +H,S04€ 0SO3H @) Hex-3-ene vapour evolved is collected and condensed. 349POLYMERIZATION Polymerization is the coupling together of many small molecules (monomers) into a large one (polymer) with or without the elimination of simple molecules such as HO, HCI or NH. Types of polymerization According to the mechanism involved, polymerization can be divided into two basic types: (A) Addition polymerization ‘The monomers add together to form polymer molecules without climination of small molecules. The monomers involved are compounds having a carbon-carbon double bond. Examples of addition polymers CN CNH leet Tea toc H-C=C-H 1 I H B/y vinyl cyanide Orton Note: nisav ible, large number. (B) Condensation polymerization ‘This usually occurs between two different types of monomers, each cone being at least bifunctional in the same group. The monomers are joined together with elimination of small molecules such as HzO, HCI, NH etc Examples of condensation polymers ‘Monomer used Polymer formed HH me T Sait motecule al Monomers wsed Polymer formed Smal nol cc oon A tT ohio | hhh {e-0L NON), 0 felyamide (nylon) ethene polythene °° ° 0 1 1 Hl H W0-C-0-C-oW ant HO-a-on | {C-D-C-0-0-0}, 1,0 ; ul Sesccaad "same | yee sented H-C=C-H an -_ HHA pec os anti styrene (phenylethene) polystyrene (polyphenylethene) haw Bo 1,0 ne (ormaldehy de) Ho Comal) T ecmehanl i cH ‘3 and sand for hydrocarbon eis ri ee e——eeeeereoew oO nH oH/s vinyl chloride (chloroethene) polyvinyl chloride (PVC) 350 351Thermoplastic and thermosetting polymers ‘According to the behaviour on heating, polymers can be divided into two types as follows: (A) Thermoplastic polymers ‘These are polymers which soften on heating and harden on cooling, the process of softening and hardening being repeatable any number of times. They behave in this way because they consist of chaindike molecules which are attracted only by weak intermolecular forces; a small rise in temperature can overcome these forces and bring about softening. On cooling, the process is reversed. Examples: polythene, PVC, nylon ete. (B) Thermosetting polymers ‘These are polymers which can be heat-treated only once. Once hardened, they cannot be re-softened again by heating. They behave like this because strong crossdinks (covalent bonds) firmly bind the polymer molecules to one another throughout the mass of the material, forming ‘@ giant, 3-dimensional network. They therefore have very high melting points. Examples: phenol-methanal, urea-methanal et. Example 19.11 Part of the structure of each of four polymers is represented below: (a) WH sH Cs 1 + -€—C—C—C— CC ii HanHadHGa (2) ee 0) HO HO H i 1 il il 1 ++ ~C-(CHs }s -N-C-(CH, )s -N —C-(CH3)s ~N- (c) o o o o i i i tl + -O-CH,CH; -0-C-©)-C-0-CH, CH, -O-CO)-C---- 352 (D) CH) Ho Cy HCH tot ob bobo es ie een i C-0 HH C-0H C=O H I i \ Hy cH, Hy {a) In each case, (i) draw the structural formula of the repeating unit in the polymer (ii) draw the structural formula(e) of the monomer(s) from which the polymer is made (it) indicate whether the polymer is formed by addition or condensation polymerization (tv) name any small molecules eliminated during the polymerization proces. (b) Predict, with reasons, which of the polymers A, B, C, D are thermo- plastic. Describe a simple test to distinguish between thermoplastic and thermosetting polymers. (c) Both polymer A and its monomer are soluble in dichloroethane (a solvent), Describe how you could distinguish Between these solutions by a simple chemical test. Give an equation for any reaction that takes lace. (@) The identical unit from which a polymer is made up of is called repeating unit. In the case of polymer @ (CH H Cay Nae c—e td HO, (ii) Addition polymerization _ (iv) None For polymer B: © 7° 4) C—(CHs)5—-N 0) H ° H i \ i \ HO-C-(CHh)s-N-H_ (or Cl-C—(CH)s -N—H) (Gi) Condensation polymerization {iv) Water (or hydrogen chloride) 353,(b) © 354 For polymer C: @ ° ° (o-cu,ct, -0-L.©)-€ Gi) HOCH, CH,OH and ° o oO wo Ul Le HoO-C-©)-C-OH (er cl-C-)-c-c) (Gi) Condensation polymerization (iv) Water (or hydrogen chloride) For polymer D: @ fe \ Gi) CH, tod a “oh I \ue CH (Gi) Addition polymerization (iv) None All of them are thermoplastic because they all consist of chaindike giant molecules which are attracted by weak intermolecular forces only. Heat the sample gently on a hot metal plate ~ if it softens or melts, itis thermoplasti; if it does not, itis thermosetting. Shake a little of each of the solutions with Br, /CC1y. The bromine is decolorized only by the monomer solution because the following addition reaction takes place: cH, H CH, H ea + Br —> Br-C—C-Br Id Hoa (rea) (colourless) Identification of some synthetic polymers In school laboratory, many common synthetic polymers can be identified by their melting and burning behaviour. See the following table. oe | | ers oer a cones, yy = “ ay m 2 is aaa eaaeee eae lasers shoe fia fee ear a = — ee cee al = vn Ste | eta me ' se ome Sete nse a ama S emeeee mone soe Sea fmmretqreee [ecereme emonorents mrad ager camion | curt er emo os | Sn = eee =e or uu ae Se on st el 355‘Additional tests on some synthetic polymers Nylon: Heat sample with soda lime (a solid mixture of sodium hydroxide and calcium hydroxide) in a test tube. The fumes evolved (containing ammonia and/or amine RNH,) will tum moist red litmus blue. PVC: Heat sample in a test tube. The fumes evolved (containing hhydrogen chloride gas) will tum moist blue litmus red. Suck some of the fumes into a teat pipette and bubble it intoracidified silver nitrate solution. ‘A white precipitate (AgCI) will appear. Cellulose acetate: Perform the test as described for PVC. The fumes (Containing ethanoic acid CHsCOOH) turn moist blue litmus red but have no effect on acidified silver nitrate solution. EXERCISE 19 1). Study the following list of compounds, and answer the questions below: HHH HHH ioe ites A H-C-C-C-H B H-C-C=C-H ttt U HHH H 4H H OHH fl rool c H-C-OH D H-C—C—C-H | H HOH OH HHH ° i 1 B W-C-C-¢-08 F H-C-OH 1 HHH HHO HHHO Lid rit ll G H-C-C-C-On HW H-C-C-C-C-H Ii HH HHA 356 HH HH OH (@) Which compounds are gases at room conditions? Why? (b) Which compounds are soluble in water? Why? (© Which compounds, after being dissolved in water, conduct clectrcity? Why? (@) Which compounds, after being dissolved in water, form an (i) acidic solution (i}alkaline solution? Explain. (©) Which compounds react with () sodium metal (ji) zine metal to liberate a colourless, odourless gas which gives the ‘pop sound’ test? (9, Which compounds react with sodium carbonate solution to give a colourless, odourless gas which turns lime water milky? @ Which compound, after being heated with soda4ime, gives A? (h) Which compound is an unsaturated hydrocarbon? (® Which compound decolourizes bromine water and acidified potassium permanganate solution? @) Which compounds, after being heated with concentrated sulphuric acid or aluminium oxide, give an alkene? (&) Which compound, after being dissolved in concentrated sulphuric acid and then boiled with water, gives D? (@ Which compound, after reacting with hydrogen using nickel as catalyst, gives A? (m) Which compounds react with phosphorus(V) chloride to give a steamy fume? (a) Which compound, after being heated under reflux with excess acidified potassium dichromate solution, gives G? (0) Which compounds, after being heated with ethanoic acid together with concentrated sulphuric acid, give a sweet-smelling product? 357(p) Which compounds, after being heated with ethanol together with concentrated sulphuric acid, give a sweet smelling product? (@ Which compounds give a red-orange precipitate on being heated ‘with Fehling’s solution and a silver mirror with Tollens’ Reagent? (®) Which compound, after being heated with concentrated sulphuric acid, forms a combustible gas which burns with a blue flame? (8) Which compound, after being boiled with dilute acid, gives F and Gas products? (1) What isthe relationship between D and £? 2) The following account about some classes of organic compounds is found in a student's note-book. Point out where it is incomplete or incorrect: (@) Allalkanes (@ are gases at room conditions because the van der Waals’ forces among the molecules are very weak; (i) cannot decolourize bromine under any conditions because they are saturated and cannot undergo addition reactions as for alkenes. (b) Ail alkanols (alcohols) (are soluble in water because they can form hydrogen bonding with water; i) can turn red litmus blue because they give many OH ions in water; (ii) canbe dehydrated by heating with excess concentrated sulphuric acid to form alkenes; (iv) can react with aqueous sodium hydroxide or sodium carbonate to form sodium alkoxide (RON«*); (W) can be oxidized in two steps: first to alkanal and then to alkanoic acid. (©) All alkanoic acids (i can decolourize bromine water immediately because there is a carbon-oxygen double bond which can undergo addition reaction with bromine water; (i) are non-reducing. 358 3) Without referring to data books, list the following compounds in increasing order of boiling point. Explain how you artive at the result. A GH B CH, © CHOW D C3H;COOH —-—ECHsCOOH 4) Refer to the following compounds and answer the questions which follow: A CH,COOH B CH,CH,OH = -C_- HCOOH D CH,CICOOH = CC,COOH F 1,0 (@) Which group is the acidic group common to all these compounds? (b) Show tre change which takes place when the group referred to in (a) acts as an acid. (©) Explain why acid strength of these compounds differs. (@) Arrange the compounds in increasing order of acid strength. Explain your reasoning. 5) When butanol is vaporized and passed over heated pumice stone, ‘one mole of water is eliminated from each mole of the alcohol. (@) Give the name and structural formula of each of the two possible structunl isomers which result from the reaction given above. (b) One mole of each of the isomers in (a) reacts with one mole of bromine. Give the name and structural formula of each of the products. 6) Give the name(s) and structural formula(e) of the alcohol(s) which on dehydration would yield each of the following alkenes as the major product, (@) But-Lene (0) But2ene (©) 2methyipropene 7) @) State the conditions under which the following reaction will proceed readily: C,HsOH + CH,COOH —> CH;COOC;Hs + H,0 (b) With reference to the equation given in (a), write an equation for the reaction 359CHOW between CHOH and [}-COOH, where [—}epresents 2 OH, 08 large alkyl group. (©) What type of organic compound is the main product in (b)? (@) Write an equation to show the reaction between the main product in (b) and sodium hydroxide solution. (HKCEE) 8) Describe how you would distinguish between the following pairs of substances using simple chemical tests: (@) Propane and propene (b) Propan-1-ol and propanoic acid (©) Methanoic acid and ethanoic acid (@) Methanal and methanoic acid (©) Ethanol and ethyl ethanoate (f) Methanol and ethanol (®) Propanal and propan-2-ol 9) Describe a chemical method you would use to separate a mixture of propan-l-ol and propanoic acid into pure compounds in a school laboratory. 10) Suggest reaction schemes for the following conversions (reagents used and brief experimental conditions should be included): (@) Ethanol to 1,2-dibromoethane (b) Ethanol to ethane-1 2:diol (©) Propan-t-0l to sodium propanoate (@) Ethanol to methane (©) Ethanol to ethy! ethanoate (0 Ethene to ethanoic acid (© Ethene to ethanedioic acid (h) Propan-t-ol to I chloropropane (@_Propan-1-0l to 2-chloropropane (@ Propan-1-ol to propan20l 360 11) The diagram below shows the balland-stick model of an organic molecule Q. @ x00 avn © hydrogen atom (@ Name the organic compound represented by the model (b) Give the structural formula and name of the compound isomeric with @. 12) Give the names and structural formulae of the structural isomers of C.Hy OH. (HKCEE) 13) Give the names and structural formulae of the structural isomers of (@) CsHyCl (©) CHCl, (You may assume all the isomers to be open-chained.) 14) A compound X was found to be composed of only carbon and hhydrogen in the ratio of 1 mole of C atoms: 2 moles of H atoms ‘The molecular mass of X is 56, Give the names and structural formulae of all the possible structural isomers for X. 15) The following table shows the results obtained from experiments to find the number of moles of each kind of atom present in 100 g ‘each of three different compounds, P, Q and R. c H ° 1 | Molecular mass Pp | 43s | 129 | 247 | 46 (| sez |eeo2 eee 27, 85 R | 312 | 4 | 3a2 | - 32 (@) Work out the molecular formula of each compound. 361(b) One of the compounds has no isomers. Which one? (©) For the rest, draw structural formulae of all possible isomers. 16) A hydrocarbon M contains 85.7% carbon. Its vapour density is 28. (@) Calculate the empirical formula and molecular formula of M. (b) Write three possible structural isomers for M and give a name for each of them. (HKCEE) 17) A colourless organic liquid, L, contains 40.00% of carbon, 6.67% of hydrogen, and 53.33% of oxygen. 1.50 g of L, when vaporized, is found to occupy 560 cm? at s.t_p. Calculate the empirical and molecular formula of L. Write two structural formulae of compounds ‘with this molecular formula, and name these compounds. (HKCEE) 18) 1.2 g of a gaseous hydrocarbon Z are burnt completely in excess of dy oxygen in a suitable apparatus, and the resulting gas is led through concentrated sulphuric acid. The acid increases in mass by 1.86 g. Caleulate the empirical formula of Z 2.0 dm? of Z, when measured at s.t.p., weigh 5.178 g. Deduce the molecular formula of Z. Write structural formulae for the isomers of Z and name them. (UKCEE) 19) A colourless organic liquid M, with molecular formula C;H.0, gives the following reactions: (a) When M is heated with acidified potassium dichromate solution, the solution turns from orange to green. (0) When a piece of sodium is added to M, a colourless gas is given ‘off which burns with a ‘pop’. Deduce what M is, and give explanation and equations for the reactions, (HKCEE) 20) 2.3 g of a compound of carbon, hydrogen and oxygen were completely ‘burt in oxygen, 4.4 g of carbon dioxide and 2.7 g of water being formed. Find the empirical formula of this compound. If the molecular ‘mass ofthis compound is 46, find also its molecular formula, ‘The above compound can react with alkanoic acid to give a product which possesses a fruity smell. What is the structural formula and name of the compound? 362 Give equations to show the reactions when the above compound reacts with the following reagents: (@) Sodium metat (©) Phosphoris(V) chloride (©) Ethanoic acid (@) A mixture of potassium dichromate solution and dilute sulphuric acid. 21 ‘A compound P containing only carbon, hydrogen and oxygen gave, ‘on analysis, the following figures: C: 48.76%, H: 8.16% (by mass); vapour density = 37. Deduce its empirical and molecular formulae, Write the structural formulae of three substances which possess this molecular formula. The compound was boiled with sodium hydroxide solution, the resulting solution evaporated to dryness and the residue warmed with concentrated sulphuric acid. A combustible gas Q which burned with 4 blue flame was produced. Give the names of P and Q, and wite ‘equations forall the reactions involved. 22) When 15 cm? of a gaseous hydrocarbon A were mixed with 70 cm? of oxygen (an excess) and ignited inside a graduated tube in the presence of concentrated sulphuric acid, the volume of the residual {88 was 47.5 cm°. This was reduced to 17.5 cm? by treatment with caustic potash. All volumes were measured under the same conditions of temperature and pressure. Find the molecular formula of the hydrocarbon H. Give its name and structure. (HKCEE) 23) Prolonged oxidation of an alcohol P produces a substance Q. When Q is treated with sodium hydroxide solution and the resulting solution obtained evaporated to dryness, the remaining solid, on being heated with sodadime, gives a hydrocarbon R 56 cm? of R require 112 cm? of oxygen for complete combustion, 56 em? of carbon dioxide being produced. Give the names and structural formulae of P, Q, R and write equations for all the reactions involved. 36324) [Aldehyde] stageT, [Fatty acid] stage, [Ester x y CH,COOC;Hs ‘An ester of the formula CH, COOC; Hs can be obtained from aldehyde Xin two stages I and I In stage I, aldehyde X is converted to fatty acid Y, and in stage I fatty acid Y is converted to the ester (@) Name X and ¥. (b) What chemical(s) would you use to react with X in stage 1? Give ‘an equation for the reaction. Name the type of reaction occurring in stage I. (© What chemical(s) would you use to react with ¥ in stage I to ‘obtain the ester? Give an equation for the reaction. Name the type of reaction occurring in stage Il (@ What would happen when a piece of magnesium ribbon is added toY? (HKCEE) 25) Compounds ¥ and Z ate alkanols of molecular formula CH (CH; ),OH, ‘where x is the number of (CH, ~-) groups in the molecule. Y cannot be dehydrated by concentrated sulphuric acid to an alkene but Z can bbe dehydrated by concentrated sulphuric acid to propene. (@) What is the value of x in ¥? (b) Name ¥. (©) Write an equation to show the reaction between Y and sodium. ‘Name the products (@ What is the value of x in Z? (©) Name Z. (© Write an equation to show the dehydration of Z by concentrated sulphuric acid to propene. @ Write an equation to show the reaction between aci potassium dichromate solution and Z. Name the products. (HKCEE) fied 364 26) butanol heat hot cone. W380 ‘The above apparatus was set up by a student for the preparation of an organic gas X. Butan-I-ol in tube A was heated in an oil bath. ‘The alcohol vapour was passed through tubes B and C containing hot concentrated sulphuric acid and water respectively. A colourless gas X was finally collected in the glass syringe D. (@) State the name of gas X. (©) Using structural formulae, give the chemical equation for the conversion of butan-1-ol to gas X. (©) Why did the student prefer to use an oil bath to heat the butan- Lol? (@ What was the purpose of using hot concentrated sulphuric acid in tube B? (©) What was the purpose of using water in tube C? (What would be observed when gas X was passed into a solution of bromine in tetrachloromethane (carbon tetrachloride)? Write an equation for the reaction. © Starting with the gas X collected in syringe D, describe briefly, with the help of a diagram, how this gas could be dried and then collected. (HKCEE) 27) A is an alcohol of formula CH, (CH; OH. ‘When 6.0 g of A is treated with excess sodium, a gas is liberated which ‘occupies a Volume of 1.12 dm? measured at s.p. (Molar volume of a gas at s.t.p.= 22.40 dm?) 365(@) Write an equation for the reaction between A and sodium. (©) Calculate the formula weight of A. (©) Hence determine the value of x. A may be readily converted to an acid B by treatment with excess acidified potassium dichromate solution. When B is neutralized with sodium hydroxide solution and the resulting solution is evaporated to dryness, a solid Cis obtained. (@ Give the names of B and C. (©) Write equations for the conversion of A to B and of B to C. (© What would be seen when A is converted to B using acidified potassium dichromate solution’ @ If the neutralization of B with sodium hydroxide solution is carried out by titration, what indicator should be used? Give the colour change at the end point. (h) If 60 g of A had been completely converted to acid B, calculate the volume of 0.2 M sodium hydroxide solution required to neutralize the amount of B formed. (HKCEE) 28) The following chart shows the reactions of a compound A with several reagents “earbon 2-methylpropane alkanoic acid D acidified KMnO,, | Ha,Ni, heatunder refx | heat wae] ©HsC00H, ‘sweet |, conc.HgSO. excess conc. [alkene smelling "heat under L4 J “HySO,,heat|_B liguia¢ | heat G@) Give the structural formulae and names of compounds A, B, C and D. (©) What are the names of the reactions when A is changed to B, C and D respectively? (©) Write the equation and name the product(s) formed when A reacts with a piece of sodium. Is this reaction more vigorous than that between sodium and water? Why? 366 29) The following chart represents a series of chemical reactions. Hel E ° (Ho) cone. HsS0., 130°C K,Cr,0,/H™ excess K Crz07/H"_ a Tat 2 | pcmcia LS Pel Me F | + steamy fumes H+ |G (@) Give the structural formulae and names of compounds A to G. (b) What is the relationship between compounds £ and F? (©) What is formed when compound D reacts with cold concentrated sulphuric (@) Can compound A be formed by boiling the product formed in (©) with water? (©) Name the type of reaction forthe following conversions: @ Awe @ Awd (iA toF () DoE © C06 30) A mixture of methyl propanoate and sodium hydroxide solution {s heated for about half an hour in set-up I. Then the remaining solution is distilled in set-up IL. (See diagrams on next page.) (@) What type of reaction takes place in set-up 1? (b) Give the equation of this reaction and name the products formed. (©) Why is the water condenser necessary in setup I? (@) What should be added to the flask in set-up I to promote smooth boiling of the solution? (©) What willbe left in P after distillation in set-up II? Why? (©) What will be the organic product in the distillate Q? (@) Suggest a method to purify the organic product in Q. (a) P contains a salt and other substances. How can you isolate the salt as an acid? Write equations to show the reactions that occur. 367thermometer Q water out water out \s r water condenser water in+ <4 P mt methyl propanoate sodium hydroxide sion cat @ Setup I Setup t 31) The following chart represents a series of chemical reactions starting i from A which is an ester. a i (CaHg02) t boil with NaQH(aq) then di apenas ree Sale containing 8 containing] LE # POG + C1] aciiy with ute | pasevapourof C HSO,, then distil over heated Al, 03 eite|[Game) (Gi conttining D(CrH402) 368 (@) Give the names of A, B and C. Write the structural formula for A. (b) Draw a labelled diagram of the apparatus you would use to separate C from B. (©) Why can C be separated from B by distillation? (a) Give the name of the reagent which can be used to convert C to E. What is observed when tis reagent is added to C? (© What is the product formed when C is heated with acidified potassium permanganate solution? (f) Describe briefly how you would perform an experiment to combine C and D to form A. (Diagram is not required) HKCEE (CDC) Write a chemical equation for the reaction, 32) The structures of two possible synthetic (soapless) detergents are shown below. The zigzag line represents a hydrocarbon chain (e@,/\\y -- represents pan cu, CH...) ca cH cy betegenra \yAM-805 Detergent B AVWVVVV\— OS05"Na* (@) Does the term ‘soapless’ imply that synthetic detergents do not form lather in water? Explain. (b) State how the structure of a soapless detergent (i) resembles to (@) differs from that of a soap. (©) Soap has been used as a cleaning agent for a very long time, yet, it has been replaced considerably by soapless detergents, especially in the laundry industry. Why? (@ Most soapless detergents are made using compounds obtained from the petrochemical industry. (@_ State two types of compounds that may be used. (i) Suggest a chemical very often used to attach an ionic ‘head’ to these compounds. (©) Which of the detergents A and B is () straightchain (i) biode- gradable? (O) Would you expect detergent A to be on market nowadays? Why? 36933) 34) 370 ‘The following chart represents a series of chemical reactions starting from an organic compound P whose molecular formula is C;HsOCl. Q, R and S are all organic compounds. An aqueous solution of R ‘turns methyl orange into red colour. KMn0,/H™ P Na R | Feavunder flax | (CHOC) eae exces conc. H, SO, 180°C s (@) Give the structural formulae and names of P, Q, R and S. (b) Which of P, Q, R and S can be polymerized? Write an equation to show the polymerization and name the polymer formed. A HH BHO I 1 il H-C-C-OH H-C-C-OH It i HH H c aa _ Nel al H-C-C-H H-C-C-N-H i im HH HH E ° Pee el 4 i i f i HO~C-(CH;)n—C-OH H-N—(CH, )y-N-H Gc ua ial H-C=C-H (@) Which of the above substances would you use to prepare: (an addition polymer? Gil) a condensation polymer? (b) Draw diagrams to indicate the structure of these two polymers, in each case showing three monomer molecules linked, 35) Here is a list of substances: cellulose, urea-smethanal, nylon, PVC, terylene, ethene, ethyl chloride, ethane. From this ist, name: (@) a naturally occurring polymer (©) a synthetic polymer (©) a thermoplastic addition polymer (@) a thermoplastic condensation polymer (©) a thermosetting condensation polymer (© a substance which is not a polymer but can readily be converted into one (@ a substance which is not a polymer and which cannot polymerize (h) a substance which is a polymer and can be converted to another polymer. 36) Polymers consist of units repeated throughout the chain. These units are derived from the monomers from which the polymers are made. —CH, ~CH—CH, ~CH—CH, ~CH— 6 HOH HOH to to -C-01-€-N-A-N-C-0-C-N-A-N— Orlon i oot Oze 0) 0 0 Nylon (@ From the information of polymerization of vinyl chloride to polyvinyl chloride (PVC) HH HHHH 1 rit an C=C—>| -C-C-C-C— ie teste ie HC HaHG/o (Draw the structural formula of the repeating unit in Orlon, 371(i) Draw the structural formula of the monomer from which Orlon is made. (Gi) State whether Orlon is made by addition or condensation polymerization. (©) @ Draw the structural formula of the repeating unit in Nylon (@) Draw structural formulae of the monomers from which ‘Nylon is made. (ii) State whether Nylon is made by addition or condensation polymerization. (CDC. Sample Question) 37) With reference to the structural formula of polythene, consider the structure of the following polymer: R oH R H R H robot ot ot oo —c--—c¢ ——¢ _¢ ec ee eee eerie cooH H = COOH HCOOH where R is an alkyl group. (@) Draw the structural formula of the repeating unit in the polymer. (©) Draw the structural formula of the monomer from which the polymer is made. (©) Write an equation to show how the monomers combine to form the polymer. (@) Write an equation to show how the monomer reacts with @ hydrogen, (@) methanol, (i) magnesium. State the conditions necessary for each reaction to occur. (HKCEE) 372 38) A, B, C and D are four different synthetic polymers (plastics). Small bors ofthese plymes mere heated, and the folowing observations made. ‘Dube Smet! peraiowronteatng | smote | Smet ‘tes and char around _ e ro mroke | burning woo the edges: aa vo moke | fy | etemaadtanciea | mmetene | vee mete sens tofom ae nd | hte umes | be chars on the bottom — (@) Which are thermoplastic polymers? Explain your choice. (b) Which polymer could be cellulose acetate? (©) The white fumes given out by heating D form dense white clouds fon contact with ammonia. Suggest what D may be and explain your answer, (@) Which one of these four polymers would be the best choice for ‘making handles of Kettles? Give the name of a polymer suitable for this purpose. HKCEE (CDC) 373QUALITATIVE 0 ANALYSIS OF 2 INORGANIC COMPOUNDS QUALITATIVE ANALYSIS OF INORGANIC COMPOUNDS ‘The purpose of qualitative analysis is the identification of substance(s) present in a given sample. . For exercises in inorganic qualitative analysis, the substances given are usually salts and sometimes free elements, metal oxides and hydroxides, acids and so on. ‘The following tests are useful in elementary analysis: (A) Preliminary tests (B) Tests for anions (C) Tests for cations PRELIMINARY TESTS OF SUBSTANCE 1. Colour and general characteristics Probable inference (not a definite conclusion) hydrated copper({l) salts hydrated iron(II) or copper(I) salts, chromates, hydrated iron(ltl) salts, Observation Blue colour Green colour Yellow colour PbO, PoIz, Ast Brown colour hydrated iron(II) salts Purple colour ‘permanganates Orange colour dichromates Black colour some sulphides (e.g. FeS, PbS, CuS, Ag2S), some oxides (¢.g. Fes0s, CuO), etc. ‘Smell of ammonia ammonium salts, ammonia solution Deliquescence some chlorides (e.g. CaCl, FeCls), some nitrates (e.g. NaNO), NaOH, KOH 374 2. Salabiy in wate terol (0) All ommon sts of pots, sod and Tnoninn () All common tates nd (©) Al hyéropen carbonate (8) All common ctr bromides and iodides oer those of ser) and (e) All common sulphates ° except: barium sulphate and lead(II) sulphate (CaSO, is sparingly soluble) Water-insoluble (©) Most acids and acidic oxides (@) All common carbonates except those of potassium, sodium and (h) All metal hydroxides except those of potassium, sodium and ammonium. (Ca(OH), is slightly soluble) 3. Action of litmus paper Solutions of acids, acidic oxides, most acid salts and salts cerived fom strong acid and weak tase (€g, CuSO.) tum bie litmus re Solutions of ass and sls derived fom weak acd and stom base (¢.g. CHCOONa) turn red litmus blue. ° Bleaching agents (e.g. Cl,) turn litmus paper white * Lead) halides are insoluble in cold water but soluble in hot water 3754, Action of heating solid sample strongly Observation Inference Yellow sublimate sulphur Violet vapour and dark grey iodine shiny sublimate Dark red sublimate FeCl White sublimate ammonium halides, AICI; ete. Water vapour evolved hydrated salts; hydrogen carbonates; some hydroxides some hydrated salts Fe,0, formed (from decomposition of iron compounds) CuO formed (from decomposition of copper(II) compounds) ZnO formed (from decomposition of zinc compounds) PbO formed (from decomposition of lead compounds) some ammonium salts some carbonates; hydrogen carbonates ammonium nitrate some sulphides nitrates and nitrites (except those ‘of potassium, sodium and ammonium) nitrates (except NHNO;); some oxides of metals (eg. PbO2, He0, ‘Ag, 0); chiorates (e.g. KCIOs) sulphites (except those of sodium ‘and potassium); some sulphates Colour change Rust red residue Black residue from blue or green sample Residue yellow when hot, white when cold Residue orange when hot, yellow when cold ‘Ammonia evolved Carbon dioxide evolved Dinitrogen oxide evolved Hydrogen sulphide evolved Nitrogen dioxide evolved Oxygen evolved Sulphur dioxide evolved 5, Flame test Certain metals or their salts give flames with distinctive colours. Observation Inference Brilliant golden yellow sodium compounds Lilac (crimson through cobalt potassium compounds blue glass) Brick red calcium compounds Grey or bluish grey lead compounds Bluish green ‘copper compounds Apple green ‘barium compounds 376 6. Heating with sodium carbonate or sodium hydroxide solution Observation Inference Ammonia evolved ammonium salt 7. Action of dilute sulphuric acid or hydrochloric acid Gas evolved Inference Carbon dioxide carbonates or hydrogen carbonates Hydrogen sulphide sulphides Nitrogen dioxide nitrites Sulphur dioxide sulphites 8 Action of concentrated sulphuric acid ‘The “ollowing gases and/or vapours may be evolved, besides those mertioned in test 7 Gases} evolved Inference Hydrogen chloride chlorides Hydrogen bromide and bromine bromides Hydrogen iodide and iodine iodides [Nitric acid and nitrogen dioxide nitrates 9. Action of acidified potassium permanganate Observation Inference Purple colour discharged reducing agents present e.g. Fe(II) compounds, sulphites ete. Properties and tests for gases Colour ad and odour Tests) Equation ‘Ammonia | colourless; turns moist red | NH3(g) + HCI(a) characteristic | litmus blue; forms | = NH, CI) smell dense white fumes with hydrogen chloride 377Colour Colour Gas pa Tests) Equation Gas Cm =a ra Bromine [reddish brown | turns moist starch | Bra) + 21 Gq) Nitogen | brown; turns starch iodide vapour; iodide paper blue | + 2B (aq) + I(2q) dioxide | characteristic | paper blue characteristic (ls turns starch smell smell dark blue) Oxygen | colourless; Telights a glowing Carbon | colourless; turns lime water | Ca(OH), (aa) codourless splint dioxide | odourless milky eee Sulphur | colourless; tums K;C0, | 580,*(aq) 2003(6)+ H20@) dioxide | smell of burning | paper from + 2Mn0s(a9) Carbon | colourless; bums with a pale | 2CO() + 05) sulphur orange Golden | + 6H"(aq) monoxide | odourless blue flame to | —» 2CO2(g) yellow) to green; |—> 580¢"(aq) form a gas which decolourizes +2Mn™"(aq) turns lime water aE + 31,008) = Water colourless; tums anhydrous | CuSO.) + 51,0@) Chiorine | pale yellowish | turns moist blue | Cl, (@) + H, 0) vapour | condenses on cold | copper(t) — CuS04.5H;063) green; smell of | litmus paper red, | —> HCI(aq) surface to give | sulphate from bleaching solution | then bleaches it +HCIO(aq) colourless drops | white to blue; (bleaches itmus of liquid turns blue Paper) cobalt(I) chloride Hydrogen [ colourless; tums with a pale | 2H,@) + 0.08) paper pink odourless blue flame and a | —> 2H,0(@) : ee ae rage iiydrogen | Forms steam forms dense white + Ni hone | fumes im most | fumes th NH | —> NHC) White equations and sate be changes forte folowing: airy acrid smell (a) Dilute sulphuric acid is added to solid sodium carbonate Tiydrogen colourless; tums KiCrn0, | HaS@) (b) Dilute hydrochloric acid is added to iron(II) sulphide, sulphide | smell of bad eggs | paper from + (CH; COO),Pb(aq) (¢) Concentrated sulphuric acid is added to solid copper(II) nitrate and wee eae ea oc the mixture is heated strongly. tums lead acetate | +2CH, paper shiny black “a (d) Concentrated nitric acid is added to copper. isaisogaea | oni vapour pee | ca SN a {e) Solid ammonium chloride is warmed with sodium hydroxide solution. vapour | characteristic’ | or strchiodide (f) Zine carbonate is heated. smell paper blue Dinstogn | colourless; faint | relight « lowing (@)_NazC0s(6) + H$04(ag) —> Na, $04 (aq) + CO (2) + Hs 0) oxide | sweet smell splint There is effervescence, a colourless, odourless gas being evolved. Nitrogen | colourless tums brown in | 2NOG) + Ox(@) () FeS(6) + 2HCI(aq) —> FeCl; (aq) + HS) monoxide air — 2N0.6) 378 ‘There is effervescence, a colourless gas with a smell of bad eggs being. evolved. 379(©) Cu(NO5), (6) + HzS04 (2) —> CuS04 6) + 2HNOSG@) 4HNO,(8) —> 4NO2(g) + O2(8) + 2H 008) ‘A vapour is evolved, which condenses to liquid on sides of test tube. The vapour turns brown as heating continues. (a) Cu(s) + 4HNO3(aq) —> Cu(NO5), (aq) + 2NO3(g) + 2H2 O(8) Brown fumes are evolved, and solution in the test tube becomes blue. (@) NHaCI(s) + NaOH(aq) —> NaCl(aq) + NHs(g) + H:0(®) ‘A colourless gas with characteristic pungent ‘ammonia’ smell is evolved. (f) ZnCO5(s) —+ Zn0(s) + CO2(g) Residue (Zn0) is yellow when hot, white when cold. TESTS FOR ANIONS The following tables give characteristic reactions of some common anions. (In each case, let the sample to be tested be called X) Chloride Bromide Todide 1. Solid. ‘HCI (steamy fumes) | HBr+ Br, evolved HI I, evolved + cone. H,$0,, | evolved ex. ee eg warm [NaCl(s) + H; SO. (8) | NaBr(s)+ 1, $048) | Nal(s)+ #480408) = NaHSO,(6) | —> NaHSO.G) | —> NaHSO.() + HOw) +HE@) +H) some HBr (steamy | some HI (steamy fumes) oxidized | fumes) oxidized to Br, vapour |to fy spout Grown) Gites 2 Gy evolved ‘vapour evolved |, vapour evolved 1) +H,S040) | Br) + HS06@) [F) + H,5048) uso.) = | Hs01@) | Hs0.6) +HA@) + HBr) + HG) Mn0;()+4HC. [MnO (6)+4HBr | MnO, 3) + 4H "MnCl (aa) | MnBrs(aq) | —> Mn aq) +h) + Bn) +h@) + 2#,08) $28, 0@) +2H,00@) 380 Ghloride Bromide Todide 3. G@) Aqueous X [white curdy Tale yellow curdy | yellow cardy + AeNO, opt. (Ae) | pot. (AaB) pot. (Ag) solution |Ag"G@a)+ Crag) | Ae’aa) + Brag) | Agen) + Maa) acc) | Agnes) | > Ao) 0) Ppt. from (9 ‘+4iL HNO, lppt. insoluble | ppt. insoluble _| ppt. insoluble © Ppt ftom @) + NH ppt. soluble pot. sparingly | pp. insoluble tolution soluble 4. Aqueous X [no visible change | orange bottom | violet bottom +, water layer (due to” | layer (ue to +ct., colour of Bry | colour of fx shake Gissolved in Cc.) | aisolved in CCL) 2Briaa)+ Chg) | 21 %e9)+ Ch (aa) = Brag) | Islaq) +2cran +2CTe@) Sulphate Suiphite Sulphide 1. G@) Aqueous X [white ppt. 6aS0.) | white ppt. S05) + *Ba(NO; )Ba*tag) +50." (eq)| aaa) +S05"G@4) rotation" |—* BaS04(s) | —* B1S0366) (©) Ppt. from(a)[pp. insoluble | ppt. soluble, with +, HNO, cvolution of SOs B,S0s6)#21"(@9) — bea) +11,505 0) + H,08) +508) 2, Solid x Ino visible change | $0; evolved H, 5 evolved ai HCL 80s") 2H"(aq) | 2H°%aq)+ $*1aa) 180,09) | HS + #00) +5034) * Allematively, BaCl, solution could be used. But with chloride, Ag) (or PD«I)) salts form a white precipitate insoluble in dilute cid ‘06. 2AgNO(aq) + BaCl aq) —> 2AECIG) + Ba(NO) (oq) 381Nitrate Nitrite 1. *Brown Ring Test brown ring formed no brown ring; the whole solution turns dark brown 2. Solid X + dil. HCl | no visible change ‘NO; (brown fumes) evolved W'G@q) + NOs(@q) — HNO3(a9) 3HNNO, (aq) — HNO, (aq) + 2NO(@) +100) 2NO(G) + 03() — 2N036) 3. Solid ¥ +a NO, evolved ‘NO; evolved + eonc.H;80s, | NOs(3)+H;S04(®) | (equations 2s above) heat — HINO, +150. (6) Cu(s) + 4HNO} — Cu(N0s), (aq) +2N03(8) +2H20(0) 4. X(olid or aqueous) + acidified KMn0, solution no visible change purple colour discharged *To the aqueous sample add a solution of FeSO, and then run in concentrated H,S0, slowly to form a bottom layer. A broven ring forms at the junction of the two liguid layers in presence of a nitrate. 382 Carbonate Hydrogen carbonate 1, Solid X + dil. HCI | effervescence, COs effervescence, COs evolved evolved 2H"(aq) + CO5*(aq) | H'(aq) + HCO3 (aq) = 1,0) +C0,@) | — 1,0(8)+C05(8) 2. Aqueous X ‘white ppt.(MgCOs) | no visible change (Forma- +MgSO, solution | Mg?(aq)+CO,*(aq) —> MgCO5 (8) tion of soluble Ma(IHCOs 8 white ppt. formed on boiling. Mg*"(aq) + 2HCOs(aq) —> Ma(HCOs ) (ag) Mg(HCO; ) (aq) —L-+ MgCO3 (5) + CO3() +H,00) TESTS FOR CATIONS Action of sodium hydroxide solution To the aqueous sample add sodium hydroxide solution in small quantities at 2 time until sodium hydroxide is present in excess Observation Inference ‘A colourless gas with ‘ammonia’ ammonium salt smell (ammonia) given off on warming White precipitate, insoluble in calcium or magnesium salt excess White precipitate, soluble in excess aluminium, zine or lead({I) salt Dirty green precipitate, insoluble in iron({f) salt excess Reddish brown precipitate, insoluble —_ion(IIf) salt Pale blue precipitate, insoluble in copper(I) salt Dark brown precipitate, insoluble silver salt 383Hydroxides of aluminium, zinc and lead are amphoteric and dissolve in excess sodium hydroxide to form complex salts. Pb?(aq) + 20H(aq) — POH) Pb(OH),(s) + 2NaOH(aq) © —> 2H, O(2) + Na;PbO, (aq) sodium plumbite (or Po(OH),(s) + 2NaOH(2q) —> Naz [Pb(OH),] (#4) Zn**(aq) + 20H (ag) = Zn(0H).66) Zn(OH),(s) + 2NaOH(aq)_- —> 2H; 0(@) + NayZn0; (aq) sodium incate (or Zn(OH)(6)+2NaOH(aq) —> Na; (Zn(0H)s] (aq) ) Al"(@q) + 30H(aq) — AVOH)s6) ‘AI(OH);(6) + NaOH(aq) > 2H, 0(2) + NaAlO, (aq) sodium aluminate (or AM(OH),() + NaOH(@q)_ —> Na[AI(OH).} (aa) ) ‘Ag‘(aq) ions do not form AgOH(s) with OH'(aq). The reaction taking place is: 2Ag"(aq) + 20H'(aq) —> Ags 0(6) + H,0(2) Action of ammonia solution To the aqueous sample add ammonia solution in small quantities at a time until ammonia is present in excess. Note: NH,(g) + water > NH, (aq) NH (aq) + Hy O(@) * NHy"(aq) + OH"(aq) Observation Inference White precipitate, insoluble in ‘magnesium, aluminium or lead(I) excess salt White precipitate, soluble in excess zine salt. Green precipitate, insoluble in excess iron(II) salt Reddish brown precipitate, insoluble iron(II) salt Pale blue precipitate, soluble in excess copper(I) salt to give a deep blue solution Dark brown precipitate, soluble silver salt in excess to give a colourless solution Zine hydroxide, copper(II) hydroxide and silver oxide dissolve in excess ammonia solution to form complex compounds. 384 Cu" (aq) + 20H1(aa) = Cu(OH266) Ca(OH)a(s) + 4NHy(aq)_—— + (CUQNH)] (OH), (aq) deep blue tetraamminceopper({T) hydroxide Zn*"(aq) + 20H (aq) — 2n(OH);(s) ‘Za(OH):(6) + 4NHy(aq)—— —> [Za(NH)g] (OH) (09) colourless tetraamminezine(II) hydroxide Ag, 0(5) + H, OR) + 4NHy(aq)— 2[Ag(NHs ja] “(aq) + 20H (aq) colourless diamminesilver(I) ion Tests to distinguish between iron(II) and iron(II) salts “Tron salt (ac Fe**(ac ‘Reagent added Fee) oo NaOH(@q) dirty green gelatinous | reddish brown gelatinous precipitate of Fe(OH), | precipitate of Fe(OH)s formed, slowly turning | formed brown on standing Ks[Fe(CN).] aa) | (ale blue precipitate) | dark biue precipitate potassium (rPrussan blue) formed hhexacyanoferrate(II) K3[Fe(CN)s](aq) | dark blue precipitate | (brown coloration; potassium (*Tumbull’s blue) | no precipitate) hexacyanoferrate(II1) | formed KCNS(eq) no visible change blood-red coloration potassium (due to [Fe(CNS)] (aq) thiocyanate formed) + Prussian blue and Tumbull’s bie are infact identical (having the same composition). Confirmatory tests for lead(Il) salts To the aqueous sample, add ( dilute sulphuric acid: a white precipitate (PbSO,) formed i) dilute hydrochloric acid: a white precipitate (PbCI,) formed, which is soluble in hot water (ii) potassium iodide solution: a yellow precipitate (Pbl:) formed (iv) potassium chromate solution: a yellow precipitate (PbCrO,) formed 385‘Outlines of systematic qualitative analysis of cations For systematic analysis, the cations are divided into 6 analytic groups. (Do ‘not confuse these with the groups of the Periodic Table.) They are precipitated successively from solution as insoluble compounds by the successive addition of various group reagents, The cations of cach group, after precipitation, are removed from the solution by filuation before the nent group reagent is added. ‘The identification of individual fons in a group then depends upon a further examination of the precipitate Test Possible precipitates Group 1 Insoluble old solution AAgCl (white) chlorides + dilute HC PCI, (white) HaCl, (white) Group 2 Sulphides pass HS into a Cus (black) Insoluble in acid solution acdied with PBS (back) et, solution dilute HCI Group 3 Insoluble hydroxides warm solution with a Fe(OH), (reddish brown) Gt low oF few drops of **eonc. AU(OH), (white) ete, concentrations) HNO, add excess. NH.Cl and then [NH (aq) until atkatine Group 4 Sulphides insoluble pass HyS into a ZnS (dirty white ot. in alkaline solution solution made alkaline with ammonia solution Group $ Insoluble carbonates add (NH),COs (CaCO, (white) Solution to'a solution BaCOs (white) ete ‘made alkaline with smmonia solution and containing NH, Cl If no precipitate occurs in Group 1 to $, the ion present is probably K*, Nat or Me** (Group 6). * This scheme is nor required by the HKCE syllabus and is for reference only. HNO, is added to oxidize any Fell) present to Fe(ll). Fe(OH), will not be precipitated at low OH” concentrations, 386 Example 20.2 The following dilute aqueous solutions are available: HzS0s —-HNOs FeO, FeNOs)s Quch, Nis PYNOs): —— K3COs Choose from these solutions those which fit each of the descriptions siven below: a) One solution which gives a white precipitate with aqueous silver nitrate (b) One solution which gives a brown precipitate with aqueous silver nitrate (c) Four solutions which give a white precipitate with aqueous barium chloride. (a) Two solutions with a pH value greater than 7. {e) Four solutions which give @ precipitate with aqueous sodium hydroxide, (1) One solution which gives a dark blue precipitate with aqueous potassium hexacyanoferrate(Il). (e) Six solutions which react with magnesium meta. {h) Two solutions which react with each other. {i) One solution which gives a lilac flame in flame test {i} One solution which decolorizes aqueous potassium permanganate. (a) Cuch, (©) K,CO, (6) Hy$0s, FeSOs, Po(NOs)s KsCOs (@) NU, KzCOs (©) FeSOx, Fe(NOs)s, CuCl, PbINOs), (9) Fe(NOs)s (g) H;S0,, HNO,, FeSO,, Fe(NO3)s, CuCl, Pb(NOs)2 (b) H,S0, and K;CO, (other examples may be given) @ K:C0s (FeSO. Example 203 Give @ test t0 distinguish between the substances in each of the pairs listed below: (Give equations where appropriate) 387(a) Zinc carbonate and zine nitrate (b) Sodium sulphate and sodium sulphite (e} Copper(It) oxide and manganese(1V) oxide (d) Aluminium sulphate and zine sulphate fe} Aluminium oxide and zine oxide. (@) Add ditute hydrochloric acid to each separately, 2nCO, gives a colourless, odourless gas ZnCOs(3) + 2HCKaq) —+ ZnCla(aq) + CO2(G) + HO) No gas is given out in case of Zn(NOs ) (b) Add dilute hydrochloric acid to each separately. Na, SSO gives @ gas which has smell of burning sulphur. NapSO3(5) + 2HCi(aq) —> 2NaClf(aq) + $02(g) + H20(@) No gas is given out in case of NazSO, (©) Add moderately concentrated sulphuric acid to each separately. CuO dissolves to give a blue solution. CuO(s) + H;$04(aq) —> CuSO¢(aq) + H,0(@) blue There is no visible change in ease of MnO>. (An alternative method is to add concentrated HCI to each. MnO ‘would react to give a yellowish green gas (Cla) on heating. For CuO, there is no such change.) {@) Add ammonia solution dropwise to solutions of the two salts separately. In case of aluminium sulphate solution, a white gelatinous precipitate ‘of aluminium hydroxide is formed, which is insoluble in excess ammonia solution. Al" (aq) + 30H(aq) — A1(OH3(8) In case of zine sulphate solution, a white gelatinous precipitate of zinc hydroxide is formed. The precipitate dissolves in excess ammonia 10 form a colourless solution, due to formation of the complex ion ~ tetraamminezine(I) ion, (2n(NHs J}? ‘Zn**(aq) + 20H"(aqg) —> Zn(OH)a(s) Zn(OH)a(s) + 4NHy (aq) —> [Zn(NH3)_]*"(aq) + 20H (aq) (@) Heat the solids. Zine oxide is yellow when hot and white when cold, while aluminium oxide remains white no matter cold of hot. 388, Example 20.4 You are provided with 5 unlabelled bottles A, B, C, D and E, each containing @ colourless aqueous solution. These are’ 1'M solutions of ammonia, ethanoic acid, sodium hydroxide, sodium carbonate and nitric acid, Given some test tubes and nothing else, describe how you could label the bottles correctly. (Tasting is NOT considered ax an acceptable ‘method.) Ammonia (say from bottle A) has a characteristic pungent ‘ammonia’ ‘smell. Thus it ean be identified by its smell Ethanoic acid (say from bottle B) has a sinell of vinegar. Thus it can be identified by its smell. Mix the remaining solutions in pairs (C and D, C and £, D and E) and look for temperature rise and/or effervescence. Note that the test tube will get warm when there is an appreciable temperature rise in the solution it contains. Just feel the bottom of tube by the hand to detect any temperature rise. The pair (say from bottles C and D) which shows @ temperature rise ‘but without effervescence is a mixture of sodium hydroxide and nitric acid. The temperature rise results from the heat of neutralization, The pair (say from bottles D and £) which effervesces is a mixture of nitric acid and sodium carbonate, since carbon dioxide gas is evolved when a carbonate reacts with an acid. (There is also a temperature rise inthis case.) Thus the one common to both pairs (solution from bottle D) is nitric acid. It follows that bottle C contains sodium hydroxide solution while bottle £ contains sodium carbonate solution. Example 20.5 When a white powder L is heated with sodium hydroxide solution, @ gas M is given off which turns red litmus paper blue. On heating this compound alone, a colourless gas N which relights a glowing splint is evolved. What are L, M and N? Write equations for the reactions involved. 1, is ammonium nitrate, NHNOs M is ammonia NH NV is dinitrogen oxide ,N2O Equations: 'NH,NO3(6) + NAOH(aq) —+ NaNO (aq) + NH (g) +H 0(8) ‘NH, NO3(s) —* N20(g) + 2H; 0(@) 389Example 20.6 W, X, Y, Z are four aqueous solutions with pH values of 5, 11, 1 ‘and 14 respectively. Two of them are mixed together in turn in the exact proportions for complete reaction and the results are shown below. W x Y With X |white precipitate; neutral solution left With Y |white precipitate; | a colourless, odourless| lacidic solution left | gas evolved; neutral solution left With Z |white precipitate; | no reaction; ‘no visible change; neutral solution left | alkaline solution left | neutral solution left (a) What type of substance is solution Y? Explain your reasoning. (b) Suggest what Z may be. Give your reasoning. (e) The white precipitate formed when W reacts with Z is soluble in excess alkali, State three possible cations which this precipitate ‘may contain. (d) The precipitate obtained when W reacts with Y is soluble in hot water but reappears as colourless needle-shaped crystals on cooling. What is this precipitate? (e) What cation does W contain? Hence suggest what solution W may be (A) Suggest what ¥ may be. (g) State five anions that can react with Y to produce a gas. (h} Suggest which anion X contains. Give your reasoning. (i) Hence name the precipitate obtained when W reacts with X. (i) What may be the substance dissolved in X? (@) ¥ is a strong acid. The solution has a low pH, suggesting that it is a strong acid. (b) Sodium hydroxide (or potassium hydroxide) solution. The pH of solution Z is 14, suggesting that itis solution of a strong alkali (©) Aluminium(ttt) (AL), zine(H) (Zn?*) and lead) (Po?*) 390 (©) Lead(t chloride (P6C1), (©) Lead({I) (Pb*"). W may be Jead(I1) nitrate solution. (PbSO, , PbCl, are insoluble in water.) (0) Yis hydrochloric acid. (g) Carbonate (CO;"), hydrogen carbonate (HCO;), sulphite I) sulphide ($*) and nitrite (NO, ) ase Gon. (h) X effervesces with Y (hydrochloric acid) to give an odourless gas which should be CO, (S03, H2S and NO; all smell strongly). Hence X may contain carbonate or hydrogen carbonate. But from its relatively high pH (11), we can deduce X to be a carbonate solution. @_Lead(it eabonate. @)_ Sodium carbonate or potassium carbonate Example 20.7 ‘Some information about four unknown elements A, B, Cand D is given in the tabie below: 4 B c D Appearance |bleck powder | yellow powder | grey granules| dull grey ribbons ‘Action of lit slowsasit | it melts and | dt burns with| it burns with reat wems, some | then bums with| a bric-red | a dazaling Ihowery sparks | apale blue | flame to give | white fame cing given | flame(a awhite — | togiea sila colour. | colourtess gas | powder as | white lesigas Xis | Y with a product | powderas levetved) characteristic product choking smell is evolved) Approximatd pH of an aqueous solution of | 6 2 u 9 combustion product 391(a) Classify A, B, C and D as metals and non-metals from the pH values ‘of aqueous solutions of the combustion products. (b) Suggest what A, B, Cand D may be. fe) Suggest what X and ¥ may be. {d) What would happen when burning D is put into a gas jar containing ‘gas Y? Explain your answer. fe) What would happen when gas X is bubbled through an aqueous solution of the combustion product of C? Explain your answer. (a) The combustion products are mainly oxides. Metal oxides, if soluble in water, would react with water to give alkalis (pH > 7). Most non-netal oxides would react with water to form acids (pH < 7). ‘Thus A and B are non-metals; C and D are metals, (b) A: carbon, B: sulphur, C: calcium, D: magnesium. (©) X: carbon dioxide, ¥: sulphur dioxide. (@) Magnesium (D) continues to bum in sulphur dioxide (Y) with 2 white flame, forming white smoke. White and yellow specks of solid are formed on the sides of the jar. 2Ma(a) + $021) —> 2MgO() + S(9) wale yelow Buming. magnesium is hot enough to liberate free oxygen from sulphur dioxide and thos continues to burn inthe gs, (©) The combustion product of C is calcium oxide, which reacts with water to form caleium hydroxide, Calcium hydroxide is only slightly foluble in water — the dear solution obtained by filtration is called ime water. Ca0(s) + HzO) —* Ca(OH), (aq) Lime water would turn milky when carbon dioxide is bubbled through it Ca(OFH (ag) + COs(@) —> CaCOs(s) + H2O®) Example 208 ‘A student performs some experiments with a mixture. A, of two ‘metals. His notes on the experiments are recorded below: (a) Mixture A is partly soluble in dilute hydrochloric acid to give Iydrogen and a colourless solution B. 392 (b) Solution B gives a white precipitate with ammonia solution. The precipitate is soluble in excess of ammonia solution, (c) Mixture A dissolves completely in concentrated nitric acid to give @ brown gas C, and a greenish-blue solution D. Excess of A is used to ensure that there i no excess of concentrated nitric acid in solution D, (d) After acidification with dilute hydrochloric acid, solution D gives @ black precipitate with hydrogen sulphide. After filtration, the filtrate is made alkaline with aqueous ammonia, A white precipitate is now formed on passing hydrogen sulphide, ‘Suggest which two metals are present in mixture A. Explain all the observations, giving equations except in part (c). (HKCEE) (@) shows that one of the two components of mixture (say metal X) can displace hydrogen from acids and the other one (say metal Y) cannot. ‘Therefore X is above hydrogen in the Electrochemical Series and is below hydrogen, (b) shows that the salt solution from X gives a white precipitate with ammonia. The precipitate is soluble in excess ammonia and should be zine hydroxide. Therefore X should be zine. © shows that a greenish-blue solution is obtained when metals X and ¥ react with nitric acid. Only copper(I) ions are greenish-blue, so Y should be copper. ‘Therefore the two metals present in A are zinc and copper. ‘The observations can be further explained as follows: (a) Part of the mixture, zinc, reacts with hydrochloric acid to give hydrogen and a colourless solution of zine chloride Zn(8) + 2HCKaq) —r ZnCla(aq) + Ha(@) (©) When reacting with ammonia solution, zinc chloride forms zine hydroxide which is soluble in excess ammonia solution (due to formation of tetraamminezinc({}) ions). 2n°*(aq) + 20H"(aa) —> Zn(OH) 368) ‘Zo(OH),(8) + 4NHs(aq) —> [Zn(NHs Je] “(aq) + 20H (aq) (© Both zine and copper dissolve in concentrated nitric acid to form 1 brown gas (nitrogen dioxide) and a nitrate. Zinc nitrate is colourless and copper(II) nitrate is greenish-blue in aqueous solution. 393(@ When hydrogen sulphide is bubbled into a solution of copper(t) nitrate and zine nitrate, black copper(II) sulphide is. precipitated Out. Zine sulphide is soluble in acidic medivm but not in alkaline ‘medium. Therefore it precipitates out as a white precipitate when the solution is made alkaline and then hydrogen sulphide pased CuP(aq) + $*(aq) — Cus) ‘Zn*(aq) + S*(aq) —> ZnS(s) Example 209 Compound X contains one of the cations and one of the anions listed below: Cations: K*, Fe, C1", PO™. Anions: HCO;, $03", NOs, CT. Three tests are performed on X, and the results are tabulated below:— Test Result 1, Heat solid X. No reaction [2. Add water to solid X. X dissolves 10 form a colourless solution. |3. Add dilute hydrochloric | No precipitate is formed and ‘acid to a solution of X. no gas is evolved. (a) Deduce from test 1 only which of the above listed anions should not be present in X. Explain your answer. (Equations not required) (b) Deduce from test 2 only which of the above listed cations should not be present in X. Explain your answer. fe) Deduce from test 3 only which of the above listed anions and cations should not be present in X. Explain your answer and give ionic equations (4) By considering your answers to (a), (b) and (c), state which ions are ‘actually present in X. (HKCEE) (@) HCO and NO; should not be present, because all hydrogen carbonates and nitrates undergo thermal decompositions. (b) Fe?* and Cu should not be present, because solutions of their compounds have colours, most probably green and blue respectively. 394 © HCOs and SOs" should not be present in X because they will for: 428 with hydrochloric acid, HOQsTaa) + Haq) —> Hr0( + COxG) S05*(aq) + 2H"(aq) H20(®) + S02(g) Pb? should not be present because lead(II) ions would precipitate with CI"in the HCl added. Pb*(aq) + 2C1'(aq) ——> PDCl,(s) (@) K" and CY are actually present in X, Example 20.10 The following chart represents a series of chemical reactions, solid solid Eg A blue precipitate heat D concentrated NOs aon srcen NatiCo3 blue precipitate | solution ¢ a A brown gas F is given off in the formation of B from A, (a) Give the chemical names for A, B,C, D and E. () Give the name of a gas which can be used to convert F to A. Give the chemical equation. (¢], Give one method which can be used to obtain E from D. Give the equation, (d) What can be seen when a piece of zine metal is put into solution B? Give an ionie equation. (e) If gas F dissolves in water, what is the effect of the solution on lierus paper? 395(f) What can be seen when ammonia solution is added to D? (8) Give the chemical equations for the following changes: (i) C10 E, (i) B to D. (HKCEE) (@) A is copper; B is coppex(I) nitrate solution; Cis copper(II) carbonate; Dis copper(ll) hydroxide; is copper(I) oxide. (b) Hydrogen. (Note: Carbon monoxide, coal gas, ammonia or any other reducing gas can also be used) CuO(s) + H2(g) —> Culs) + H20(@) (©) Heat. Cu(OH);(s) — CuO(s) + HO) (@ Zine dissolves, blue colour of solution fades, and a reddish brown solid is formed. Za(s) + Cu™(aq) —> Zn*(aq) + Culs) (@) It tums moist blue litmus paper red. (The gas F is nitrogen({V) oxide (nitrogen dioxide) which reacts with water to form nitric acid and nitrous acid.) (©). D dissolves to form a deep bine solution. (@) @ CuCOs(s) — Cu0G) + COs) i) Cu(NOs)s(aq) + 2NaOH(aq) —> Cu(OH)2(s) + 2NaNOs (aq) combustion 396 A gas G is evolved when concentrated hydrochloric acid is added 10 solid potastium permanganate. G then passes over a coil of red hot iron wire placed in the combustion tube. Excess G is passed into dilute sodium hydroxide solution. (i) What is G? (ii) Why is potassium permanganate used? (iti) What happens when G passes over the coil of red hot iron wire? Give ar equation for the reaction. (iv) Why is it desirable to pass G into dilute sodium hydroxide solution? (v) What s formed when G reacts with dilute sodium hydroxide solution? Give an equation. (vi) Why isan inverted funnel used? (6) When iron{it) sulphate is strongly heated a mixture of sulphur dioxide and sulphur trioxide is given off according to the following equation:— 2FeSO, —> Fez03 + $01 + $05 (i) The gaseous mixture is passed into water. Name and give the formulke of the ions produced. (ii) Barium chioride solutton ts added 10 the solution in (i). A white precipitate appears. Name the compounds present in the precipitate, Write ionic equations for their formation. (iii) What tappens when dilute hydrochloric acid is added to the precipitate and the resulting mixture gently warmed? (iv) What happens if dilute sulphuric acid replaces ditute hydrochloric ‘cid in jit) above? Explain your answer. (HKCEE) @) @ Gischborine (i) KMnO, is used to oxidize conc. HCl to Cl; gas. (ii) Iron wire glows and dark brown fumes (FeCl, ) are formed which solidify to give dark red (black) crystals on colder parts of tube, 2Fe(s) + 3Cla(g) —> 2FeCl (8) (iv) Sodium hydroxide solution is used to react and remove the excess cchlorine passing out of the tube. (Chlorine is poisonous and should not be allowed to escape into laboratory.) (¥) Sodium hypochlorite and sodium chloride are formed. ‘2NsOH(aq) + Cl(aq) —> NaClO(aq) + NaCl(aq) + H0(@) 397(vi) Inverted funnel is used to prevent ‘sucking back’; it also provides a larger surface for chlorine to react with sodium hydroxide solution, (©) @ Hyéroxonium ions H0"(aq); sulphate ions $O,? (aq); sulphite ions $0," (aq). (ii) Ba?"(aq) + 80,7 (aq) —* BaSO«(s) barium sulphate Ba?*(aq) + SO," (aq) —* BaSO,(s) barium sulphite (Gi) Part of the precipitate (barium sulphite) dissolves in the acid, and a gas, sulphur dioxide, is evolved. $0,*(aq) + 2H"(aq) — SO.(@) + H,0@ (Gv) No noticeable change is observed because a thin layer of insoluble barium sulphate forms on the surface of the barium sulphite and prevents further reaction. EXERCISE 20 1) A small quantity of each of the following solids is heated in a test tube with a Bunsen flame. In each case, state any visible changes and write chemical equation(s) if applicable. (@)_ Ammonium chloride (b) Ammonium nitrite (©) Ammonium nitrate (@)_ Ammonium carbonate (@) Sodium nitrate (® Lead(td nitrate (8) Copper({t) nitrate (h) Silver nitrate (Sodium carbonate-10-water G)_ Calcium carbonate (k) Zinc carbonate (®) Sodium hydrogen carbonate (m) Iron(it) sulphate-7-water (a) Copper(lt) sulphate-S-water (0) Potassium chlorate (p) Red lead oxide (dilead(lt)lead(1V) oxide, PbsOa) 398 2) State visible changes and write equation(s) (if applicable) for each Of the following: (@) Concentrated nitric acid is added to copper turnings (b) Concentrated nitric acid is added to saw dust (©) Concentrated sulphuric acid is added to granular copper(II) sulphate-S-water crystals (@) Ammonia solution is added slowly to copper(I) sulphate solution until in excess (©) Sodium hydroxide solution is added slowly to zinc nitrate solution until in excess (f) A small piece of sodium (pea-sized) is dropped into a beaker half filled with water (@) Steam is passed over heated magnesium ribbon (h) Water is added to calcium oxide (0) Burning magnesium is put into a jar of carbon dioxide (@)_Buming magnesium is put into a jar of sulphur dioxide (&) Burning candle is put into a jar of chlorine (@) Dilute hydrochloric acid is added to iron(II) sulphide (m) Dilute hydrochloric acid is added to a solution of silver nitrate (a) A piece of moist blue litmus paper is put into a jar of chlorine (©) Chlorine is passed into iron({) chloride solution (p) Copper(Il) oxide placed in a hole in a charcoal block is heated directly by a roaring Bunsen flame. (@) A few drops of concentrated sulphuric acid are added to ‘one-quarter spatula measure of potassium bromide in a test tube (©) Hydrogen sulphide is allowed to mix with sulphur dioxide in the presence of water (6) Iron is put into copper(I) sulphate solution, (©) Zine is put into sitver nitrate solution (u) Barium chloride solution is added to sodium sulphite solution, followed by hydrochloric acid and then chlorine water (¥) Sodium hydroxide solution is added to iron({I) sulphate solution; the mixture is then exposed to air (w) Iron(I1) sulphate solution is added to an acidified potassium permanganate solution (X) Sulphur dioxide is passed into a solution of potassium permanganate (y) Chlorine water is added to potassium iodide solution; tetrachloromethane is then added and the mixture is shaken and allowed to stand (@) Potassium nitrate crystals are heated and a glowing splint is placed at the mouth of the tube 3993) Describe a chemical test to distinguish between the substances in each of the following pairs (@) Sodium carbonate and sodium hydrogen carbonate (b) Calcium carbonate and calcium hydroxide (©) Sodium sulphate and sodium sulphite (@) Sodium chloride and sodium nitrate (@) Potassium chloride and potassium iodide (O) Sodium nitrate and sodium bromide (@) Zinc sulphide and zinc sulphite (h) Lead({t) carbonate and zinc carbonate (Sodium nitrate and ammonium nitrate @_Copper(II) oxide and iron(tt!) oxide 4) (a) Describe simple chemical tests which would enable you to label correctly eight bottles each containing one of the following solids: sodium chloride, calcium hydroxide, calcium carbonate, sodium sulphate, calcium nitrate, sodium nitrate, ammonium chloride and potassium iodide (b) An aqueous solution of X reacts with barium chloride solution to give @ white precipitate which is insoluble in dilute hydrochloric acid. Can you conclude that X must be a sulphate? (©) Is there & precipitate formed when aqueous silver nitrate is added to (i) dilute sodium sulphate solution (ii) dilute sodium sulphite solution? 5) X is a pale green crystalline solid which dissolves in water to give a pale green solution. When barium chloride solution is added to fan aqueous solution of X, a white precipitate is formed, which is insoluble in dilute hydrochloric acid. When X is cautiously heated, water vapour is given off first. On further heating, a reddish brown solid residue is left behind. (a) Identify X. (b) Write equations for the reactions mentioned. 6) Identify the following substance A and explain all the reactions involved, giving equations where appropriate: Substance A is a colourless crystalline solid, soluble in water. When A is warmed with sodium hydroxide solution, a colourless sas is given off which turns red litmus paper blue. When A is treated with concentrated sulphuric acid, a colourless fuming gas is given off which tums moist blue litmus paper red. When a solution of A (acidified with nitric acid) is treated with silver nitrate solution, a white precipitate is formed, which dissolves readily in excess ammonia solution (HKCEE) 7) A crystalline salt X.¥.nH;0 is blue in colour. Its aqueous solution is also blue. (@ When teated, the solid salt changes to a white powder. Gi An aqueous solution of the salt gives a pale blue precipitate with aqueous sodium hydroxide. The precipitate is insoluble in excess of the alkali, but turns black on heating ii) An aqueous solution of the sat gives a similar pale blue precipitate with >. cid yellowish. Wz) solution B ween pas C silver nitrate ‘olution white precipitate ive the chemical names for A, B, Cand D. ® (b) What eagent would you use to (0) convert sodium chloride to A (ii) convert B to C? (©) Whats the effect on most pl paper of oa wm (Desert briefly how C might be converted back into 4 14) When syrupy phosphoric acid is added to sodium chloride, the gs hydrogen chloride i formed. = mi acid is added to sodium bromide, another ve eee mis ea wes dace in () water, 9 se soon a pd (a) ethylbenzene, to ie solution B olution A reacted with magnesium; slution B was found to have pocfoct on dry itmus paper. (@) What was the gas formed when syuPY with sium bromide? (@) What woud be the effect of olution A on Htmus paper? (@) What products were fomed when solution A reacted with phosphoric acid reacted ‘magnesium? (@ Would you expect solution B to react with magnesium? (©) Solution A was found to conduct clectricity, but under identical conditions, no current would flow through solution B, Explain what this result indicates. (©) When ammonia gas is passed into solution A, no visible change occurs. What happens when ammonia gas is passed into solution B? 15) lead nitate freezing mixture Niguid Later ‘The diagram shows the apparatus in which lead(II) nitrate is heated. (@) Name the liquid L and the gas X. (b) Write down the equation for the action of heat on lead(ll) nitrate. (©) What is the colour of lead(It) nitrate? (@) What is the colour of the residue after strong heating? (©) What isthe colour of liquid L? (0 If the Utube is not cool enough, a brown gas will pass into the trough of water. What is the brown gas? (a) A little of the liquid Z is heated gently first and then strongly in a stout vessel. There is a series of colour changes. Explain these changes, 405