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8/22/2016

Course Outline
K E N N E T H

Solutions and Their


Concentrations
Gravimetric Analysis
Analytical Chemistry Acid Base Equilibria
Volumetric Analysis
Engr. Kenneth Soriano

Molarity (M)
O

Molar concentration is the number of that


O Solutions and Their species that is contained in 1L of the
Concentrations
O

OH
solution
Aspirin

O OH

Stearic Acid

Part per Million (ppm) Parts per Million (ppm)

For very dilute solutions, parts per million A handy rule in calculating parts per
(ppm) is a convenient way to express million is to remember that for dilute
concentration aqueous solutions whose densities are
approx. 1.00 g/mL,

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Parts per Billion (ppb) Normality (N)

is the number of equivalents that is


contained in 1L of the solution

Normality
O O

H
Gravimetric
H H Analysis O
Anthraquinone
OH
O
Progesterone

H H

O
Testosterone

Basic Steps on Precipitation Method


Gravimetric Analysis Sample is dissolved in an appropriate
solvent.
A precipitant is used to convert the analyte
Gravimetric Method of Analysis deals into a sparingly soluble precipitate.
with the measurement of the mass of a The precipitate is converted into a product of
substance that is chemically related to the known composition by a suitable heat
analyte. treatment.
The percentage of the analyte in the sample
is calculated using the gravimetric factor (GF)

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Gravimetric Analysis Prepare Solution of the Sample


Choice of Solvent
Water ( w/ or w/o heating)
Non-Oxidizing Acids
WT.
SAMPLE
Oxidizing Acids (HNO3)
Aqua Regia (3:1 HCl:HNO3)
Fluxing Agents
Acid: K2S2O7 Redox: Na2O2
Basic: Na2CO3

Precipitation of Analyte
Elements / Ion Precipitating Final/Ignited
Precipitated Agent Form
Cl, Br, I AgNO3 AgCl, AgBr, AgI
EXCESS Fe, Al ,Cr NH3 Fe2O3 , Al2O3 , Cr2O3
DISSOLVED
PRECIPITATING
SAMPLE Mg NH4 HPO4 Mg2P2O7
AGENT
K H2PtCl6 K 2PtCl6
Ni Dimethylglyoxime Ni DMG
CaC2O4 - 110C
Ca (NH4)2C2O4 CaCO3 - 500C
CaO - 800C

FILTRATION
PRECIPITATION
AND
OF THE IGNITION
ANALYTE
OF THE
PRECIPITATE

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Gravimetric Analysis Calculations

WT.
FINAL FORM

Example Example 1
A 0.5662-g sample of an ionic compound The aluminum in a 759.08 mg of impure
containing chloride ions and an unknown aluminum sulfate sample was precipitated
metal is dissolved in water and treated as Al(OH)3 and ignited at 1100C to yield a
with an excess of AgNO3. If 1.0882 g of precipitate of Al2O3 weighing 387.953 mg.
AgCl precipitate forms, what is the percent Express the result of analysis in terms of
by mass of Cl in the original compound? %Al.
ANS. 47.54% a. 27.05% b. 13.53%
c. 18.67% d. 23.29%

Example 2
A 250 mg sample containing 45% MgCO3
and 55% CaCO3 was ignited producing
CO2 as decomposition product. Assuming
that the decomposition reaction is
complete, what is the change in weight of
a NaOH solution used to absorb CO2
ANS. 119.21 mg

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Example 3 Example 4
What weight of an impure NaCl sample A sample containing NaBr and KBr only
must be taken for analysis so that the weighs 253.02 mg. The sample was
weight of AgCl precipitate obtained in mg dissolved in water and treated with excess
will be equal to the %Cl in the sample? AgNO3. The precipitate formed was found
to weigh 429.85 mg. Calculate the %NaBr
ANS. 24.73 mg in the sample.
ANS. 49%

Example 5
A 0.6407-g sample containing chloride and O O

iodide ions gave a silver halide precipitate


weighing 0.4430 g. This precipitate was H
Acid Base
then strongly heated in a stream of Cl2 gas H H Equilibria O
Anthraquinone
to convert the AgI to AgCl; on completion O
Progesterone
OH

of this treatment, the precipitate weighed H

0.3181 g. Calculate the percentage of H H

chloride and iodide in the sample. O


Testosterone

Ans. 4.72% Cl- and 27.05% I-

Arrhenius Acids and Bases Arrhenius Acids and Bases

Arrhenius defined acids as substances Monoprotic Acid - each unit of the acid
that ionize in water to produce H+ ions and yields one hydrogen ion upon ionization
bases as substances that ionize in water
to produce OH- ions.
ARRHENIUS ACID ARRHENIUS BASE
Produces H3O+ in soln Produces OH- in soln

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Arrhenius Acids and Bases Arrhenius Acids and Bases


Diprotic Acid - each unit of the acid gives Triprotic Acid - which yield three H+ ions,
up two H+ ions, in two separate steps are relatively few in number

Arrhenius Acids and Bases Strength of Acids and Bases


Classification of Electrolytes
STRONG WEAK
1. Inorganic acids such as HNO3, 1. Many inorganic acids, including HF
HClO4 , H2SO4 (only on first HCN, H2CO3, H3BO3, H3PO4, H2S,
ionization) , HCl, HI, HBr, HClO3, H2SO3
HBrO3
2. Alkali and Alkaline-Earth (Grp I and 2. Most organic acids ( ex. HC2H3O2
II) hydroxides - KOH, NaOH, acetic acid, HCOOH formic acid)
LiOH, RbOH, Mg(OH)2, Ba(OH)2 , 3. Ammonia and most organic bases
Ca(OH)2
3. Most Salts 4. Halides, cyanides, and
thiocyanates of Hg, Zn, and Cd

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Bronsted-Lowry
Acids and Bases
Brnsted acid is a substance capable of
donating a proton, and a Brnsted base is
a substance that can accept a proton.
BRONSTED ACID BRONSTED BASE
Proton Donor Proton Acceptor

Bronsted-Lowry Bronsted-Lowry

An extension of the Brnsted definition of


acids and bases is the concept of the
conjugate acid-base pair, which can be
defined as an acid and its conjugate
HCl : Proton Donor (H+) base or a base and its conjugate acid.
H2O: Proton Acceptor

Bronsted-Lowry

The conjugate base of a Brnsted acid is


the species that remains when one proton
Conjugate means has been removed from the acid.
Conversely, a conjugate acid results from
joined together the addition of a proton to a Brnsted
base.

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Bronsted-Lowry Bronsted-Lowry
Every Brnsted acid has a conjugate
base, and every Brnsted base has a
conjugate acid. For example, the chloride
ion (Cl- ) is the conjugate base formed
from the acid HCl, and H3O+ (hydronium
ion) is the conjugate acid of the base H2O.

Bronsted-Lowry

Bronsted-Lowry Lewis Acids and Bases

Lewis base as a substance that can


donate a pair of electrons. A Lewis acid
is a substance that can accept a pair of
electrons.
LEWIS ACID LEWIS BASE
Electron Pair Acceptor Electron Pair Donor

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Lewis

Autoprotolysis of Water Autoprotolysis of Water

In 1 L, or 1000 g, of water, there are 1000 Autoprotolysis of Water


g/(18.02 g/mol), or 55.5 moles, of water.
Therefore, the concentration of water, or
[H2O], is 55.5 mol/L, or 55.5 M. This is a
large quantity compared to the
concentrations of other species in solution
(usually 1 M or smaller), and we can
assume that it does not change
appreciably during the course of a
reaction.

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Ion Product Constant p Function

Whenever [H+] = [OH-], the aqueous solution


is said to be neutral.

Example pH of Strong Acid

At 100C,whatistheneutralpHofwater?

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pH of Strong Acid pH of Strong Acid


Neglecting contribution of H2O to H3O +
function.
C
A

pH of Strong Acid pH of Strong Acid


pH of 1 x 10-7 M HCl Alternative Formula:
Using C... pH = ?
D
Using A and B pH =?

pH of 1 x 10-10 M HCl
Using A and B.pH =? E

pH of Strong Base pH of Strong Base


Calculate the pH of 1 x 10^-8 M NaOH
F
Calculate the pH of a 0.02 M Ba(OH)2
solution
G
The pH of a Ba(OH)2 solution is 10.0.
What is the H+ concentration?

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Weak Acid Acid Ionization Constant (Ka)

Percent Ionization Example


Calculate the pH of a 0.036 M nitrous acid
(HNO2) solution and calculate the %
ionization. Ka = 4.5 x 10^-4

The pH of a 0.10 M solution of formic acid


(HCOOH) is 2.39. What is the Ka of the
acid?

Example
A 0.03 M HClO2 solution is 10.0% ionized.
Calculate Ka

Ka for HC2H3O2 is 1.75 x 10-5. What is the


pH of a 0.003 M solution?

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Weak Base Weak Base

Example Common-Ion Effect


Calculate the pH of a 0.08 M NH3 solution. Common Ion Effect
Kb = 1.8 x 10-5 *is the shift of equilibrium caused by the
addition of a compound having an ion in
common with the dissolved substance
*reduction in the ionization of the weak
electrolyte

Example An important relationship between the acid


ionization constant and the ionization
Ex. Calculate the [H3O+] in a 0.005 M constant of its conjugate base can be
HC2H3O2 solution. Ka = 1.8 x 10-5 derived as follows, using acetic acid as an
example:
Ex. What is the [H3O+] in a 0.005 M
HC2H3O2 which contains 0.001 M
NaC2H3O2?

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The conjugate base, CH3COO-1, supplied


by a sodium acetate (CH3COONa)
solution, reacts with water according to the
equation

Hydrolysis Reaction of Salts


Acidic Salt: NH4Cl
NH4+ + H2O H3O+ + NH3 KH = KW/KNH3
Basic Salt: NaCN
CN- + H2O HO- + HCN KH = KW/KHCN

pH of Salts Example
Acidic Salt: What is the pH of the resulting solution
when Csalt/KH >>> 1000 made by mixing 25 mL of 0.1 M HCl and
15 mL of 0.1 M NaOH?

Basic Salt:
What is the pH of 0.256 M NH4Cl? Kb of NH3
when Csalt/KH >>> 1000
= 1.8 x 10-5?

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pHofaBufferSolution
Buffer Solutions
Solutions that contains weak acid or weak
base and its conjugate salt.
These solutions tend to resist changes in
pH.

What mass in grams of NaC2H3O2 must be What is the pH of the resulting solution
dissolved with 500 mL of 0.100 M acetic made by mixing 5 mL of 0.2178 M HCl and
acid to make 2L of buffer solution of pH = 15 mL of 0.1156 M NH3? Kb = 1.8 x 10-5?
5? Ka = 1.8 x 10-5 a. 9.49 b. 11.00 c. 9.02 d. 12.74
a. 2.28 g b. 7.19 g c. 7.38 g d. 2.12 g

O O

What volume of 0.200 M HCl must be


added to 80 mL of 0.150 M NH3 to
produce a 2L buffer solution with a pH of
H
Volumetric Analysis
H H O

8.00? Kb of NH3 = 1.8 x 10-5 O


OH
Anthraquinone

Progesterone

a. 3.2 mL b. 9.6 mL c. 28.8 mL d. 56.8 mL H

H H

O
Testosterone

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Volumetric Analysis
Standard Solution solution of known
Volumetric Methods of Analysis measures concentration
the volume of solution necessary to react
completely with the analyte

Volumetric Analysis
Primary standard
a substance
of high purity

NaOH
PELLETS

Volumetric Analysis Primary Standards for Bases


Characteristics of a Good Primary Benzoic Acid, C6H5COOH (1 OH-)
Standard Oxalic Acid, H2C2O42H2O (2 OH-)
High purity and high molecular weight Potassium Biiodate, KH(IO3)2 (1)
Stable towards air, high temperature and Potassium Hydrogen Phthalate (KHP),
humidity C6H4(COOH)(COOK) (1)
Soluble in water Sulfamic Acid (HSO3NH2) (1)
Readily available and fairly inexpensive

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Primary Standards for Acids


Calcium Carbonate, CaCO3 (2 H+)
Mercuric oxide, HgO (2) Standardization process of determining
Sodium Carbonate, Na2CO3 (2) the concentration of an unknown solution
Tris-hydroxymethylaminomethane
(THAM), (CH2OH)3CNH2 (1)

Volumetric Analysis NaOH


Solution
V mL = ?
Conditions for Volumetric Analysis
The reaction must be rapid and can be DISTILLED
WATER
represented by a simple balanced equation.
The reaction is complete and no side reaction DISSOLVED
occurs. KHP
(known amount)
An appropriate indicator must be available in INDICATOR
order to detect the end point of the reaction (Ph)
(1-2 drops)

Record the volume


Example
of NaOH consumed
In a titration experiment, a student finds
that 23.48 mL of a NaOH solution are
END POINT
Very Light Pink
needed to neutralize 0.5468 g of KHP.
Solution What is the concentration (in molarity) of
the NaOH solution?

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Example Types of Titration


How many grams of KHP are needed to Direct Titration the analyte reacts with
neutralize 18.64 mL of a 0.1004 M NaOH the standard solution directly
solution?
Back Titration an excess standard
solution is added and the excess is
determined by the addition of another
standard solution

Types of Titration Example


Replacement Titration the analyte is In standardizing a solution of NaOH against
converted to a product chemically related 1.431 gram of KHP, the analyst uses 35.50
to it and the product of such reaction is mL of the alkali and has to run back with
titrated with a standard solution 8.25 ml of acid (1mL = 10.75 mg NaOH).
What is the molarity of the NaOH solution?
a. 0.2118 c. 0.7831
b. 0.2044 d. 0.2598

Kjeldahl Method
Step 3. Titration
(Determination of Organic Nitrogen)
Using an excess amount of HCl. . .
Step 1. Digestion NH3 + HCl NH4Cl
The sample is oxidized in hot, concentrated The excess HCl is determined using a
sulfuric acid, H2SO4 and turns black. . . standard NaOH solution
Step 2. Distillation HCl + NaOH NaCl + H2O
The oxidized solution is cooled and then
treated with NaOH to liberate ammonia
gas: NH4+ + HO- NH3(g) + H2O

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Using Excess HCl Back Titration


Ammonia distilled is collected in a boric acid
(a) mmol excess reagent added solution. . .
- (b) mmol excess reagent reacted w/ back NH3 + H3BO3 NH4+ + H2BO3-1
titrant
Titrate the H3BO3-NH3 solution with standard
(c) mmol excess reagent reacted w/ acid. . .
analyte
H2BO3-1 + H3O+ H3BO3 + H2O

Using excess H3BO3 acid


Replacement Titration
Percentage Protein in the sample
*data about boric acid IRRELEVANT %protein =%N * f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)

A 5.8734-gram sample beef was analyzed A 2060 mg sample of flour was taken
for its N content and the liberated NH3 was through a Kjeldahl procedure and the
collected in a 50.00 mL of 0.4691 M HCl ammonium produced was distilled into 100
and a 12.55 mL back titration with 0.0256 mL of 0.1006 M H3BO3 solution. If this
M NaOH was required. Calculate the solution required 34.7 mL of 0.174 M HCl
percentage protein in the beef sample. for titration to methyl red end point, what is
a.17.32% b. 5.54% c. 34.64% d. 11.08% the percentage of protein in flour? Use
5.70 for flour. Ans. 23.89%

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Double Indicator Method


Mixture of NaOH, Na2CO3 or NaHCO3
A 758-mg sample of full cream milk was
Hargis
analyzed by the Kjeldahl method; 38.61
mL of 0.1078 M HCl were required to
titrate the liberated ammonia. Calculate
the % N in the sample.
a.12.04% b. 7.69% c. 15.59% d. 10.93%

Double Indicator Method Double Indicator Method


Mixture of NaOH, Na2CO3 or NaHCO3
Mixture of NaOH, Na2CO3 or NaHCO3 - no
more than two of these three constituents Skoog
can exist in appreciable amount in any
solution

Na2CO3 and NaHCO3 Na2CO3 and NaOH

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Double Indicator Method (Mixture of Bases)

A sample that may contain NaOH,


Na2CO3, NaHCO3, and inert matter alone a. 5.842% NaHCO3 and 6.577% Na2CO3
or in compatible combination is titrated
b. 6.577% Na2CO3 and 5.842% NaOH
with 0.1000 N HCl with phenolphthalein as
the indicator and the solution became c. 65.77% Na2CO3 and 5.842% NaHCO3
colorless after the addition of 48.8 mL. d. 65.77% Na2CO3 and 5.842% NaOH
Methyl orange is then added and 14.55
mL more of the acid are needed for the
color change. If the sample weighs 2.345
grams, it contains

A sample consisting of Na2CO3, NaHCO3


and inert matter weighs 1.179 grams. It is Precipitation
titrated with 0.100 N HCl with
phenolphthalein as the indicator, and the The titrant forms an insoluble product with
solution became colorless after the the analyte. An example is the titration of
addition of 24.00 mL. Another duplicate chloride ion with silver nitrate solution to
sample was titrated with HCl using methyl form silver chloride precipitate. Again,
orange as indicator. It required 50.25 mL indicators can be used to detect the end
of the acid for the color change. What is point, or potential of the solution can be
the percentage of NaHCO3 in the monitored electrically.
sample?

Precipitation Indicators in Precipitimetry


One of the oldest analytical techniques Formation of a colored secondary precipitate
that started in the mid-1800s. Silver Mohr Method (K.F. Mohr, Germany, 1865)
nitrate (AgNO3) is commonly employed in Direct Method for halides and cyanides
such technique. Titration with AgNO3 is
often termed as argentometric titration. Titrant: Silver Nitrate, AgNO3
Titration Reaction: Ag+ + Cl- AgCl(s) white
Indicator: sodium chromate, Na2CrO4

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MOHR METHOD MOHR METHOD


Indicator Reaction: What is the molar concentration of AgNO3
2Ag+ + CrO42- Ag2CrO4(s) red solution standardized against 712 mg
Primary Standard for AgNO3: NaCl primary standard NaCl (58.45 g/mol)
requiring 23.8 mL of the solution for
Titration is carried out between pH of 7-10. titration?
Usually, a low concentration of chromate
is desired to detect the endpoint clearly a. 0.5027 M b. 0.5118 M
since a chromate ion imparts an intense c. 0.5263 M d. 0.5329 M
yellow color.

MOHR METHOD VOLHARD METHOD


Formation of colored complexion
A 1.500-gram sample of impure AlCl3 was Volhard Method (Jacob Volhard, Germany,
dissolved in water and treated with 45.32 1874)
mL of 0.1000 M AgNO3 using Mohr Direct method for silver - Indirect method
method. Determine its purity as %AlCl3 for halides
(133.33)
Titrant: Potassium thiocyanate, KSCN
a. 40.28% b. 13.43%
Titration is carried out in acidic condition to
c. 4.48% d. 27.36%
hasten precipitation of ferric ion to its
hydrated oxide form.

VOLHARD METHOD Chloride in a brine solution is determined


Direct Titration Reaction: by the volhard method. A 10.00-mL aliquot
Ag+ + SCN-1 AgSCN(s) white of the solution is treated with 15.00 mL of
standard 0.1182 M AgNO3 solution. The
Indirect Titration Reaction: excess silver is titrated with standard 0.101
Ag+(excess) + Cl-1 AgCl(s) white M KSCN solution, requiring 2.38 mL to
Ag+ + SCN-1 AgSCN(s) white reach the red Fe(SCN)2+ end point.
Indicator: ferric alum Calculate the concentration of chloride in
Indicator Reaction: the brine solution, in g/L. Ans. 5.434 g/L
Fe+3 + SCN-1 Fe(SCN)+2 red

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FAJANS METHOD FAJANS METHOD


Formation of a colored adsorption complex Titration is carried out between pH of 4-7.
Fajans Method (K. Fajans, Poland, 1874) Dextrin is added to prevent excessive
Titrant: Silver nitrate, AgNO3 coagulation of the AgCl precipitate.
Titration Reaction: Ag+ + Cl-1 AgCl(s) white
Indicator: dichlorofluorescein, best for
determination of halides and cyanides
End point: color change from yellow to pink

COMPLEXOMETRIC COMPLEXOMETRIC
The titrant is a reagent that forms a water-
Ethylenediaminetetraacetic acid (EDTA) is
soluble complex with the analyte, a metal
one of the most useful chelating agents
ion.
used for titration. It will react with a large
The titrant is often a chelating agent (a number elements , and the reactions can
type of complexing agent that contains two be controlled by adjustment of pH.
or more groups capable of complexing with Indicators can be used to form a highly
a metal ion). The reverse titration may be colored complex with the metal ion.
carried out also.

Titration with Ethylenediaminetetraacetic


For metal ion in detections, it is necessary to
Acid (EDTA)
adjust the pH to 7 or above so that the
The structure suggests six potential sites blue form predominates in the absence of
(hexadentate) for metal bonding: the four a metal cation. Generally, metal
carboxyl groups and two amino groups. complexes with EDTA are red as H2In-1.
When an excess EDTA is added, the
Commercially, the free acid and the
solution turns blue according to the
dehydrate are available. Solutions of
reaction:
EDTA combines with any metal ions in a
1:1 ratio. The indicator used for titration is MIn-1 + HY-3 HIn-2 + MY-2
the Eriochrome Black T. wine red royal blue

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Example Aluminum is determined by titrating with


EDTA:
What volume of 0.0305 M EDTA is needed Al3+ + H2Y2- AlY- + 2H+
to titrate the Ca in 178.56 mg of CaCO3?
A 1.00 g sample requires 20.5 mL EDTA
a.58.54 mL b. 29.27 mL for titration. The EDTA was standardized
c. 43.91 mL d. 14.64 mL by titrating 25.0 mL of a 0.100 M CaCl2
solution, requiring 30.0 mL EDTA.
Calculate the percent Al2O3 in the sample.
Ans. 8.71%

A 1.509-g sample of a Pb/Cd alloy was dissolved


in acid and diluted to exactly 250.0 mL in a
volumetric flask. A 50.00-mL aliquot of the diluted
A masking agent is a complexing agent solution was brought to a pH of 10.0 with an
that reacts selectively with a component in NH4+/NH3 buffer; the subsequent titration involved
both cations and required 28.89 mL of 0.06950 M
a solution to prevent that component from
EDTA. A second 50.00 mL aliquot was brought to
interfering in a determination.
a pH of 10.0 with an HCN/NaCN buffer, which also
served to mask the Cd2+; 11.56 mL of the EDTA
solution were needed to titrate the Pb2. Calculate
the percent Pb and Cd in the sample. Ans. 55.16%
Pb and 44.86% Cd

Determination of Cyanide by
Example
the Liebig Method
The titration is carried by the drop wise A 500-mg sample containing NaCN
addition of AgNO3 in a solution of a required 23.50 mL of 0.1255 M AgNO3 to
cyanide forming a soluble cyanide obtain a permanent turbidity. Express the
complex of silver: result of this analysis as % CN-.
2CN- + Ag+ Ag(CN)2-1. a. 15.34% b. 23.01%
The endpoint of the titration is the c. 17.25% d. 30.67%
formation of a permanent faint turbidity:
Ag(CN)2-1 + Ag+ Ag[Ag(CN2)](s)

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Determination of Nickel
An ammoniacal solution of nickel is treated
Example
with a measured excess of standard cyanide A 750.25-mg of alloy nickel was dissolved
solution and the excess of standard AgNO3 and treated to remove the impurities. The
solution according to the reactions: ammoniacal solution was treated with 50 mL
Addition of Excess Cyanide: of 0.1075 M KCN and the excess cyanide
Ni(NH3)6+3 + 4CN-1 +6H2O Ni(CN)4-1 +6NH4OH required 2.25 mL of 0.00925 M AgNO3.
Back Titration with Ag+: Determine %Ni in the alloy.
2CN-1 + Ag+ Ag(CN)2-1 a. 20.86% b. 37.69%
Endpoint: c.10.43% d. 41.27%
Ag(CN)2-1 + Ag+ Ag[Ag(CN)2](s)

REDOX TITRATION OXIDANT


Reduction-Oxidation. These redox
OXIDANT Combining Ratio, also (f)
titrations involve the titration of an
KMnO4 (a) 5
oxidizing agent with a reducing agent, or
KMnO4 (b,n) 3
vice versa.
K2Cr2O7 6
I2 2
MnO2 2

REDUCTANT
REDUCTANT Combining Ratio, also (f)
What is the molarity of a KMnO4 solution
Na2C2O4 (C2O42) 2
FeSO4 (Fe+2) 1 standardized against 1.356 gram Na2C2O4
Na2S2O3 1 (134 g/mol) requiring 25.1 mL of the
KI 1 solution in acidic medium?
Fe metal 2
a. 0.161 M b. 0.403 M
As2O3 4
H2O2 2 c. 1.008 M d. 0.856 M
Cu+ 1

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The percentage of MnO2 in a 500 mg A 240-mg sample of pyrolusite was treated


sample which after the addition of 80.00 with excess KI. The iodine liberated
mL of 0.1056 M FeSO4 solution required required 46.24 mL of 0.1105 M Na2S2O3
8.50 mL of 0.0867 M K2Cr2O7 is solution. Calculate the % MnO2 in the
a. 33.52% b. 35.00% sample.
c. 17.50% d. 67.04% a. 46.27% b. 30.85%
c. 92.54% d. 76.12%

A 0.200-g sample of pyrolusite is analyzed for


manganese content as follows. Add 50.0 mL of
a 0.100 M solution of ferrous ammonium sulfate
A sample of iron ore weighing 385.6 mg to reduce the MnO2 to Mn+2. After reduction is
was dissolved in acid and passed through complete, the excess ferrous ion is titrated in
a Jones reductor. If the resulting solution acid solution with 0.0200 M KMnO4, requiring
required 52.36 mL of 0.01436 M K2Cr2O7 15.0 mL. Calculate the percent manganese in
for titration, calculate % Fe3O4 (231.55 the sample as Mn3O4 (only part or none of the
g/mol) in the ore sample. manganese may exist in this form, but we can
make the calculations on the assumption that it
a. 15.05% b. 45.15% does). Ans. 66.74%
c. 90.30% d. 67.98%

A hydrogen peroxide solution is analyzed


by adding a slight excess of standard A sample of a pyrolusite weighs 0.5000 g.
KMnO4 solution and back-titrating the To this is added 0.6674 g of As2O3 and
unreacted KMnO4 with standard Fe+2 dilute acid. After solvent action has
solution. A 0.587-g sample of the H2O2 ceased, the excess three-valent arsenic is
solution is taken, 25.0 mL of 0.0215 M titrated with 45.00 mL of 0.1000 N KMnO4.
KMnO4 is added, and the back-titration Calculate the oxidizing power of the
requires 5.10 mL of 0.112 M Fe2+ solution. pyrolusite in terms of percentage MnO2.
What is the percent H2O2 in the sample? Ans. 78.19%
Ans. 6.13%

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