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Stoichiometry and Chemical

Measurements
Mole
Solution
Chemical and Solution Stoichiometry
Mole

Mole ( mol)
 Is the SI unit for the amount of substance.
 Defined as the amount of a substance that contains the
same number of entities as the number of atoms in 12 g
of carbon-12. this number is called Avogadro’s number.

One mole (1 mol) contains 6.022 x 10 23 entities


Examples

1. Silver is used in jewelry and tableware but no longer in


U.S. coins. How many grams of Ag are in 0.0342 mol of
Ag?
2. Gallium is a key element in solar panels, calculators,
and other light sensitive electronic devices. How many
Ga atoms are in 2.85 x 10 -3 mol of gallium?
3. Iron is the main component of steel and, thus, the most
important metal in industrial society; it is essential in the
body. How many Fe atoms are in 95.8 g of Fe?
Examples

4. Nitrogen dioxide is a component of urban smog that


forms from gases in car exhaust. How many molecules
are in 8.92 g of nitrogen dioxide?
5. Ammonium carbonate is a white solid that decomposes
with warming. It has many uses, for example, as a
component in baking powder, fire extinguishers, and
smelling salts.
a) How many formula units are in 41.6 g of ammonium
carbonate?
b) How many O atoms are in this sample?
Definition of Solutions

• A solution is a homogeneous mixture of two or


more substances. A solution may exist in
any phase.
• Solutions consists of at least one substance,
called a solute, evenly dispersed throughout a
second substance, called the solvent.
• The amount of solute that can be dissolved in
solvent is called its solubility.

• For solutions with components in the same


phase, the substances present in lower
concentration are solutes, while the substance
present in highest abundance is the solvent.
Properties of Solutions
A chemical solution exhibits several properties:

 a homogeneous mixture.
 composed of one phase (e.g., solid, liquid, gas).
 Particles in a solution are not visible to the naked
eye and evenly distributed.
 does not scatter a light beam.
 Components of a solution do not separate upon
standing.
 Components do not chemically react with each
other.
 Concentration can be changed.
Types of Solution
Colloids and Suspensions

• Colloids are solutions of undissolved particles


that do not separate over time.
 Milk is a colloid (or colloidal mixture)
because it contains proteins and fats that do not
dissolve.
Particles in a colloid must be between 1 and
1000 nanometers in diameter.
Colloids and Suspensions

• Particles greater than 1000 nanometers in diameter


will separate from a mixture when standing. These
mixtures are considered suspensions.
Blood is considered a suspension. Blood cells will
settle in a tube upon standing because they are
greater than 1 micrometer in diameter.
Blood cells can be separated by centrifugation, a
spinning process that accelerates settling.
Main Factors that Affect Solubility

Solubility of a solute
• Is the maximum amount of solute that can dissolve
in a certain amount of solvent or solution at a certain
temperature.

Nature of the solute and solvent

The amount of solute that dissolves


depends on what type of solute it is.
Main Factors that Affect Solubility

 Temperature -- Generally, an increase in the


temperature of the solution increases the solubility of a
solid solute.
• For example, a greater amount of sugar will dissolve in
warm water than in cold water.
• A few solid solutes, however, are less soluble in warmer
solutions.
• For all gases, solubility decreases as the temperature of
the solution rises. An example of this is Soda.
• The solubility of the carbon dioxide gas decreases when
a soda is warm, making the soda flat.
Main Factors that Affect Solubility

 Pressure
 For solid and liquid solutes, changes in pressure have
practically no effect on solubility.
 For gaseous solutes, an increase in pressure increases
solubility and a decrease in pressure decreases
solubility.
Example: When the cap on a bottle of soda pop is
removed, pressure is released, and the gaseous solute
bubbles out of solution. This escape of a gas from
solution is called effervescence.
The amount of carbon dioxide that was
dissolved in the drink at a higher pressure will
not stay dissolved once the drink is opened at a
lower pressure.
Factors Affecting the Rate Of Solution

Rate of solution is a measure of how fast a substance


dissolves.

Size of the particles


• When a solute dissolves, the action takes place only
at the surface of each particle. When the total surface
area of the solute particles is increased, the solute
dissolves more rapidly.
• Breaking a solute into smaller pieces increases
its surface area and increases its rate of solution.

• The smaller the particles of solute the easier it


will fit into the spaces of the solvent
Factors Affecting the Rate Of Solution

 Stirring
• With liquid and solid solutes, stirring brings fresh
portions of the solvent in contact with the solute.
Stirring, therefore, allows the solute to dissolve
faster.
 Amount of solute already dissolved
• When very little solute in the solution, dissolving
takes place quickly.
• When a lot of solute in the solution, dissolving
takes place more slowly.
Factors Affecting the Rate Of Solution

 Temperature
• For liquids and solid solutes, increasing the
temperature not only increases the amount of solute
that will dissolve but also increases the rate at which
the solute will dissolve.
• For gases, the reverse is true. An increase in
temperature decreases both solubility and rate of
solution.
Concentrations of Solution

Concentration is defined as the amount of solute


dissolved in a given amount of solution.

• The concentration of a solution can be expressed in


different units.
• The denominator is the total amount of solution, which
includes the amount of solute.
Ways of Expressing Solution Concentration
• By mass
Percentage
• By volume
Mole Fraction (X)
Molality (m)
Molarity (M)
Normality (N)
Parts per million
(ppm)
Parts per billion
(ppb)
Percent (%)

Common units that use percent are:

1. Mass/mass percent
2. Volume/volume percent

Mathematically expressed as:


Percent Mass/Mass, % (m/m)

• This concentration unit can be determined by:


Percent Volume/Volume, % (v/v)

• This unit is typically used when liquids or gases


are the solute.

For example:
A bottle of wine that is 14% (v/v)
alcohol means that 14 mL of alcohol is
present in 100 mL of the wine.
16.2
Percent Volume/Volume, % (v/v)

• Isopropyl alcohol (2-


propanol) is sold as a
91% solution. This
solution consist of 91
mL of isopropyl alcohol
mixed with enough
water to make 100 mL
of solution.
Mole Fraction

Mole fraction (X) of a solute


 is the ratio of number of moles of solute to the total
number of moles ( solute plus solvent).
16.2
Molarity

•Molarity (M) is the number of moles of solute


dissolved in one liter of solution.

Mathematical Expression:

or

Units: moles / liter , mmoles / liter

• A unit related to mmole/L is used in the laboratory


to describe the concentrations of solutions.

1 mole = 1000 mmol


16.2
Molarity

• To make a 0.5-molar
(0.5M) solution, first
add 0.5 mol of solute
to a 1-L volumetric
flask half filled with
distilled water.
16.2
Molarity

• Swirl the flask • Fill the flask with


carefully to water exactly to the
dissolve the solute. 1-L mark.
Molality
Normality
Normality
• defined as the number of equivalents (eq) of solute
divided by the number of liters of solution containing
the solute.

• Common units of normality include N, eq/L, or meq/L.


1000 mEq = 1 Eq
• the only unit of chemical concentration that depends
on the chemical reaction being studied.

• Typically used in acid-base chemistry, redox


reactions, or precipitation reactions.
Normality (N)
Normality

Relationship of M and N:

normality = molarity x h

Types of reaction h value


Non-redox reactions
*acid No. of replaceable H+
*base No. of replaceable OH-
*salt No. of + charge ion
Redox reactions No. of electron lost or gained
Equivalent Weight

• For Acids
Example:
1N solution of HCl = MWt/z per litre = 36.5/1 per
litre
= 36.5g HCl per litre

1N solution of H2SO4 = MWt/z per litre = 98/2 per


litre
= 49g H2SO4 per litre
Equivalent Weight

• For Bases (Alkali)


z equals the number of moles of H+ ie. (HCl) that would
react with 1 mole of the base.
Example:
NaOH + H+  Na+ + H2O z =1
Ca(OH)2 + 2H+  Ca2+ + 2H2O z =2

Equivalent weight of NaOH is MW/z = 40/1 = 40 g/equiv


Equivalent weight of Ca(OH)2 is MW/z = 74/2 = 37 g/equiv
Equivalent Weight

• Ionic Reactions
(eg Precipitation Reactions) the value of z is based on
the ion charge.

Ca2+ + CO32-  CaCO3(s) z = 2

Equivalent weight of CaCO3 is MWt/z = 100/2


EWt = 50g per equivalent

Al2(SO4)3  2Al3+ + 3SO42- z = 6


Equivalent Weight
• Redox Reactions
the Equivalent Weight is based on the change in the value
of the Oxidation Number.
EWt = MWt/(number of electrons taking part in the half
reaction)
O2 + 4 H+ + 4e-  2H2O EWt = 32/4 = 8 g per equiv
Example
The COD Analysis method uses Potassium Dichromate
(K2Cr2O7 ) to oxidise the chemical constituents in the
sample.

Cr2O72- + 14 H+ + 6e-  2Cr3+ + 7H2O (half reaction)


z = 6 EWt = 294/6 = 49g/equiv
Parts per Million (ppm) and
Parts per Billion(ppb)

• Parts per million and parts per billion are concentration


units for very dilute solutions.

• The unit of ppm is referred to as 1 mg/L


and ppb is referred to as 1 μg/L.

36
Parts per Million (ppm) and
Parts per Billion(ppb)

• Multiplying a solution, given in g solute/mL solution,


by one million will provide a concentration in ppm.
• Similarly, multiplying by one billion will provide a
concentration in ppb.

37
Ways of Expressing Solution
Concentration
Examples
1. What is the molality of a solution prepared by
dissolving 32.0 g of CaCl2 in 271 g of water?

2. Hydrogen peroxide is a powerful oxidizing


agent; it is used in concentrated solution in
rocket fuel, but in dilute solution in hair
bleach. An aqueous solution of H2O2 is
30.0 % by mass and has a density of 1.11
g/mL. Calculate a) molality, b) mole fraction
of H2O2, and c) molarity.
Ways of Expressing Solution
Concentration
3. a) Find the concentration of calcium ion ( in ppm) in
a 3.50-g pill that contains 40.5 mg of Ca2+.
b) The label on a 0.750-L bottle of Italian chianti
indicates “ 11.5 % alcohol by volume”. How many
liters of alcohol does the bottle of wine contain?
c) A sample of rubbing alcohol contains 142 g of
isopropyl alcohol (C3H7OH) and 58.0 g of water.
What are the mole fractions of alcohol and
water?
4. Find the normality of 0.321 g sodium carbonate in
a 250 mL solution.
5. Calculate the normality of 0.248 mol H2SO4 dissolved
in 250 mL of solution?
Ways of Expressing Solution
Concentration
Examples:
6. Find the number of millimoles of solute in
a. 2.00 L of 2.76 x10-3 M KMnO4.
b. 250 mL of a solution that contains 4.20 ppm of
CuSO4.
7. Calculate the normality of a solution prepared by
dissolving 220.0 mg of K2Cr2O7 in 100.0 mL of water that
will be used to oxidize ferrous chloride according to the
following reaction.
K2Cr2O7 + FeCl2 + HCl  CrCl3 + FeCl3+ KCl + H2O
a. Calculate the normality
b. What weight of ferrous chloride is needed to react
completely with 50.00 mL of the K2Cr2O7 solution?
Dilution

• To prepare a solution of low concentration, you


can dilute a solution of higher concentration.

• For example, if you add water to a can of


concentrated orange juice, the amount of orange
juice does not change even though you have
more solution present.

• The amount of solute stayed the same, but the


volume increased, so the concentration of the
solution decreased.
41
Dilution

• Mathematically, a dilution equation can be expressed


as seen in the following equation:

Cinitial is the initial concentration,


Cfinal is the final concentration,
Vinitial is the initial volume, and
Vfinal is the final volume.

42
16.2

Making Dilutions
• Making a Dilute Solution
16.2

Making Dilutions
• To prepare 100 ml of 0.40M MgSO4 from a stock
solution of 2.0M MgSO4, a student first measures
20 mL of the stock solution with a 20-mL pipet.
16.2

Making Dilutions
• Then transfers the 20 mL to a 100-mL volumetric
flask.
16.2

Making Dilutions
• Finally carefully add water to the mark to make 100
mL of solution.
16.2
Making Dilutions

• Volume-Measuring Devices
16.4
16.4
Dilution
For example, if 150 mL of 0.90% saline is diluted to a
final volume of 450 mL with water, what would the
concentration of the final diluted concentration be?
Solution

50
Colligative Properties of Solution

• Colligative comes from colligate – to tie


together ( collective)
• Colligative properties of solution are
properties that depend on amount of
solute molecules or ions, but not upon the
identity of the solute.
• The effect is the same for all solutes
Chemical Composition of Aqueous
Solutions

Electrolytes
* Form ions when
dissolved in water
* Produces solutions that
conduct electricity
Strong electrolyte Weak electrolyte
*complete * Partial
ionization ionization
Classifications of Electrolytes
CLASSIFICATION OF ELECTROLYTES
STRONG WEAK
1. Inorganic acids such as 1. Many inorganic acids
HNO3, HClO4,H2SO4, HCl, including H2CO3, H3BO3,
HI, HBr, HClO3, HBrO3 H3PO4, H2S, H2SO3
2. Alkali and alkaline-earth 2. Most organic acids
hydroxides
3. Most salts 3. Ammonia and most
organic bases
4. Halides, cyanides, and
thiocyanates of Hg, Zn,
and Cd
Classification of Solutes
( electrical conductivity)
• Electrolytes
 An aqueous solution of an electrolyte conducts because
the solute separates into ions as it dissolves.
 Strong electrolytes- soluble salts, strong acids, and
strong bases- dissociate completely
 Weak electrolytes- weak acids and weak bases-
dissociate very little

• Nonelectrolytes
 Solutions which do not conduct a current such as sugar
and alcohol do not dissociate into ions at all.
Colligative Properties of Non-volatile
Nonelectrolyte Solution

 Vapor Pressure lowering


 Boiling Point elevation
 Freezing Point depression
 Osmotic Pressure: drives solvent from lower
concentration to higher concentration
Vapor Pressure Lowering

Vapor pressure of a nonvolatile nonelectrolyte


solution is always lower than the vapor
pressure of the pure solvent.

The difference in vapor pressures is the vapor


pressure lowering.
Vapor Pressure Lowering
Vapor pressure is dependent on a number of factors
including:
 the temperature of the system (kinetic energy is
required to help the molecules escape into the gas
phase),

 the pressure of the system (high pressure can keep


the gas contained in the liquid e.g. a bottle of coke),

 the intermolecular forces of the liquid itself (stronger


bonds will require more kinetic energy to break slowing
the evaporation process, lowering the overall vapor
pressure of the system).
Quantifying The Vapor Pressure Lowering:
Raoult’s Law
• Vapor pressure of solvent in solution containing non-
volatile solute is always lower than vapor pressure of
pure solvent at same T
– At equilibrium: rate of vaporization = rate of condensation
– Solute particles occupy volume reducing rate of evaporation the
number of solvent molecules at the surface
– The rate of evaporation decreases and so the vapor pressure
above the solution must decrease to recover the equilibrium
Quantifying The Vapor Pressure Lowering:
Raoult’s Law

Raoult’s Law
 The vapor pressure of solvent above a
solution ( Psolvent) equals the mole fraction of
solvent ( X solvent) times the vapor pressure of
the pure solvent (P0solvent)

P solvent = X solvent x P0solvent

P solvent = (1-X solute) P0solvent


Thus:

P0solvent - P solvent = ∆P = X solute x P0solvent


Example

• Find the vapor pressure lowering when 10.0 mL of


glycerol (C3H8O3) is added to 500 mL of water at 500C.
At this temperature, the vapor pressure of pure water is
92.5 torr and its density is 0.988 g/mL. The density of
glycerol is 1.26 g/mL.

Answer: 0.461 torr


Boiling Point Elevation

Normal boiling point of a liquid


 defined as the temperature at which the vapor pressure
of the liquid is equal to standard pressure (1 atm).

• In solution vapor pressure is reduced compared to pure


solvent
• Liquid boils when vapor pressure = atmospheric
pressure
• Must increase T to make vapor pressure = atmospheric
Quantifying Boiling Point Elevation
• Boiling point elevation is proportional to the concentration
of solute :
∆Tb = Tb (solution) – Tb (solvent) = Kbm

• When a solute is dissolved in a solvent, the boiling point


of the solution is raised according to the equation:

∆Tb = Kbm
∆Tb= change in temperature
m = the molality, which is the moles of solute per
kilograms of solvent
Kb = the molal boiling point constant
(for water, Kb = 0.5121oC/m)
Freezing Point

Normal Freezing point of a liquid


 is the temperature at which a liquid becomes a
solid at 1 atm.
Freezing point of a solution
 is the temperature at which its vapor pressure
equals that of the pure solvent, that is, when
solid solvent and liquid solution are in
equilibrium
Freezing Point Depression(∆Tf )

• Depends on the solute only being in the liquid


phase
– Fewer water molecules at surface: rate of freezing
drops
– Ice turns into liquid
– Lower temperature to regain balance
– Depression of freezing point
Quantifying Freezing Point Depression
(∆Tf )

Change in temperature is given by:

∆Tf = Tf(solvent)- Tf(solution) = Kfm

∆T = change in temperature
m = the molality, which is the moles of solute
per kilograms of solvent
Kf = the molal freezing point constant
(for water, Kf = -1.86 oC/m)
Example

• You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to


4450 g of water in your car’s radiator. What are the
boiling and freezing points of the solution?

Answer: ∆Tb = 101.85 0 C


∆Tf = -6.73 0C
Osmotic Pressure (∏)

Osmosis
 Occurs when solutions of different concentrations
are separated by a semipermeable membrane, one
that allows solvent, but not solute, to pass through.

Osmotic Pressure
 Is a net flow of solvent into a more concentrated
solution causes a pressure difference.
Quantifying Osmotic Pressure
• Osmotic Pressure is proportional to the number of solute
particles in a given solution volume, that is, to the
molarity (M)

Mathematically expressed as:

Where: R = is the universal gas constant, 0.0821 atm.L/ mol.K


T = expressed in Kelvin
Example
• Biochemists have dissolved more than 400 mutant
varieties of hemoglobin., the blood protein that carries
O2. a physician dissolves 21.5 mg of one variety in water
to make 1.50 mL of solution at 5.0 0C. She measures an
osmotic pressure of 3.61 torr. What is the molar mass of
the protein?

Answer: 6.89 x 10 4 g/mol


For Strong Electrolyte Solutions
{van't Hoff factor (i)}

 If the solute is an ionic species (a salt) then it is


most likely going to split up into its component
ions when it hits the solvent (normally water). If
this is the case, each particle that forms must
be considered.

van't Hoff factor (i) and must be used whenever


colligative properties of solutions containing ions
be calculated.
van't Hoff factor (i)
Where :
i = is the number of particles into which the solute
dissociates

Example:
For Non electrolyte:
sucrose i = 1 [no dissociation]
For strong electrolyte:
NaCl i = 2 [NaCl → Na++Cl-]
K2SO4 i = 3 [K2SO4 → 2K+ + SO42- ]
Quantifying Colligative Properties for
Strong Electrolyte Solutions

• For Vapor pressure lowering :


∆P = i ( Xsolute x P0 solvent)
• For Boiling Point Elevation:
Δ Tb = imKb

• For Freezing Pt. Depression:


Δ Tf = imKf
• For Osmotic Pressure:
Example

• A 0.952-g sample of magnesium chloride dissolves in


100g of water in flask.
a) what is the amount ( mol) represented by each ions?
b) Assuming the solution is ideal, what is the freezing
point ( at 1 atm)?
Stoichiometry of Reactions in Solution

Steps of converting the volume of reactant or product in


solution to amount ( mol):
 Balance the equation.
 Find the amount (mol) of one substance from the volume
and molarity.
 Relate it to the stoichiometrically equivalent amount of
another substance.
 Convert to the desired units.
Example
Road Map

Mass (g) of Mg(OH)2

Divide by MW (g/mol)

Mole of Mg(OH)2

Molar ratio

Amount ( mol) of HCl

Divide by M ( mol/L)

Volume (L) of HCl


Example

• Mercury and its compounds have uses from fillings for


teeth ( as a mixture with silver, copper, and tin) to the
production of chlorine. Because of their toxicity, however,
soluble mercury compounds, such as mercury (II) nitrate,
must be removed from industrial wastewater. One
removal method reacts the wastewater with sodium
sulfide solution to produce solid mercury (II) sulfide and
sodium nitrate solution. In the laboratory simulation,
0.050 L of 0.010 M mercury (II) nitrate reacts with 0.020
L of 0.10 M sodium sulfide. How many grams of mercury
(II) sulphide form?
Example

• What mass of Ag2CO3 (276 g/mol) is formed


when 25.0 mL of 0.200 M AgNO3 is mixed with
50.00 mL of 0.0800M Na2CO3?

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