Analytical chemistry

Analytical chemistry is the study of the separation, identification, and

quantification of the chemical components of natural and artificial materials.

- Qualitative Analysis gives an indication of the identity of the chemical species

in the sample.

- Quantitative Analysis determines the amount of certain components in the

substance.

The separation of components is often performed prior to analysis.

Analytical methods can be separated into classical and instrumental.

Analytical methods can be separated into:

1- Classical methods use separations such as precipitation, extraction, and

distillation and is achieved by ;

Qualitative analysis by color, odor, or melting point.

Quantitative analysis by measurement of weight or volume.

2- Instrumental methods use an apparatus to measure physical quantities of the

analyte such as light absorption, fluorescence, or conductivity.

The separation of materials is accomplished using chromatography, electrophoresis

or Field Flow Fractionation methods.

Qualitative Analysis refers to analyses in which substances are identified or

classified on the basis of their chemical or physical properties, such as chemical
reactivity, solubility, molecular weight, melting point, radiative properties (emission,
absorption), mass spectra, nuclear half-life, etc.

Quantitative Analysis refers to analyses in which the amount or concentration of an

analyte may be determined and expressed as a numerical value in appropriate units.

Qualitative Analysis may take place without Quantitative Analysis.

Quantitative Analysis requires the identification (qualification) of the analyte for

which numerical estimates are given.

Several ways have been developed in quantitative analysis to identify the components
like Gravimetric analysis and Volumetric analysis.

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Gravimetric analysis
Gravimetric analysis describes a set of methods for the quantitative determination of
an analyte based on the mass of a solid.

- Precipitation: the analyte must first be converted to a solid by precipitation with an

appropriate reagent. The precipitate can then be collected by filtration, washed, dried
to remove traces of moisture from the solution, and weighed. The amount of analyte
in the original sample can then be calculated from the mass of the precipitate and its
chemical composition.

- Vaporization: analyte may be removed by vaporization then collected and

measured directly. Or, the sample can be weighed before and after it is dried; the
difference between the two masses gives the mass of analyte lost. This is especially
useful in determining the water content of complex materials such as foodstuffs.

Volumetric analysis
Volumetric titration is a common laboratory method of quantitative chemical
analysis that is used to determine the unknown concentration of an identified analyte.

Volumetric analysis can be simply a titration based in a neutralization reaction, a

precipitation or a complex forming reaction as well as a titration based in a redox
reaction.

In neutralization reactions, the reaction occurs between an acid and a base, and
yields a salt and water

In the precipitation reactions the standard solution is in the most cases silver
nitrate which is used as a reagent to react with the ions present in the sample and
to form a high insoluble precipitate.

Complex forming titration is a reaction that occurs between metal ions and a
standard solution that is in the most cases EDTA (ethylene diamine tetra acetic
acid).

In the redox titration the reaction is carried out between an oxidizing agent and a
reduction agent.

Standard solution
A standard solution is a solution containing a precisely known concentration of an
element or a substance i.e., a known weight of solute is dissolved to make a specific
volume. Standard solutions are used to determine the concentrations of other
substances, such as solutions in titrations. The concentrations of standard solutions are
normally expressed in units of moles per litre (mol/L, often abbreviated to M for
molarity).

2
A simple standard is obtained by the dilution of a single element or a substance in a
soluble solvent with which it reacts.

A solution of acid can be standardized by titrating it against a solution of alkali of

known concentration. Once this has been calculated, it can in turn be used as a
standard solution to find the concentration of a solution of alkali.

The standard solution is a reference guide to discover the molarity of unknown

species.

Titration
8
Titration is a common laboratory method of quantitative chemical analysis that is
used to determine the unknown concentration of an identified analyte. Since volume
measurements play a key role in titration, it is also known as volumetric analysis.

3
 A reagent, called the titrant is prepared as a standard solution. A known
concentration and volume of titrant reacts with a solution of analyte to determine
concentration.

4
Types of titrations
- Acid-base titrations

Acid-base titrations depend on the neutralization between an acid and a base when
mixed in solution.

In addition to the sample, an appropriate indicator is added to the titration chamber,

reflecting the pH range of the equivalence point.

The acid-base indicator indicates the endpoint of the titration by changing color.

The endpoint and the equivalence point are not exactly the same because the
equivalence point is determined by the stoichiometry of the reaction while the
endpoint is just the color change from the indicator. Thus, a careful selection of the
indicator will reduce the indicator error.

When more precise results are required, or when the reagents are a weak acid and a
weak base, a pH meter or a conductance meter are used.

- Redox titrations

Redox titrations are based on a reduction-oxidation reaction between an oxidizing

agent and a reducing agent.

A potentiometer or a redox indicator is usually used to determine the endpoint of

the titration, for instance;

When the oxidizing agent is potassium dichromate. The color change of the solution
from orange to green is not definite, therefore an indicator such as sodium
diphenylamine is used.

Analysis of some compounds for sulfur dioxide requires iodine as an oxidizing agent.
In this case, starch is used as an indicator; a blue starch-iodine complex is formed in
the presence of excess iodine, signalling the endpoint.

Some redox titrations do not require an indicator, due to the intense color of the
constituents. For example, in permanganometry a slight faint persisting pink color
signals the endpoint of the titration because of the color of the excess oxidizing agent
potassium permanganate.

- Gas phase titration

Gas phase titrations are titrations done in the gas phase, specifically as methods for
determining reactive species by reaction with an excess of some other gas, acting as
the titrant. In one common the gas phase titration, gaseous ozone is titrated with
nitrogen oxide according to the reaction

O3 + NO → O2 + NO2

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- Complexometric titrations

Complexometric titrations rely on the formation of a complex between the analyte and
the titrant. In general, they require specialized indicators that form weak complexes
with the analyte. Common examples are Eriochrome Black T for the titration of
calcium and magnesium ions, and the chelating agent EDTA used to titrate metal ions
in solution.

- Zeta potential titrations

Zeta potential titrations are titrations in which the completion is monitored by the Zeta
potential, rather than by an indicator, in order to characterize heterogeneous systems,
such as colloids. One of the uses is to determine the iso-electric point when surface
charge becomes zero, achieved by changing the pH or adding surfactant. Another use
is to determine the optimum dose for flocculation or stabilization.

- Assay

An assay is a form of biological titration used to determine the concentration of a

virus or bacterium. Serial dilutions are performed on a sample in a fixed ratio (such as
1:1, 1:2, 1:4, 1:8, etc.) until the last dilution does not give a positive test for the
presence of the virus. This value is known as the titer, and is most commonly
determined through enzyme-linked immunosorbent assay (ELISA).

Endpoint and equivalence point

Equivalence point is the theoretical completion of the reaction: the volume of added
titrant at which the number of moles of titrant is equal to the number of moles of
analyte, or some multiple thereof (as in polyprotic acids).

Endpoint is what is actually measured, a physical change in the solution as

determined by an indicator or an instrument mentioned above.

There is a slight difference between the endpoint and the equivalence point of the
titration. This error is referred to as an indicator error, and it is indeterminate

Measuring the endpoint of a titration

Different methods to determine the endpoint include:

Indicator: A substance that changes color in response to a chemical change. An

acid-base indicator (e.g., phenolphthalein) changes color depending on the pH.
Redox indicators are also used. A drop of indicator solution is added to the
titration at the beginning; the endpoint has been reached when the color changes.

Potentiometer: An instrument that measures the electrode potential of the

solution. These are used for redox titrations; the potential of the working electrode
will suddenly change as the endpoint is reached.

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pH meter: A potentiometer with an electrode whose potential depends on the
amount of H+ ion present in the solution. The pH of the solution is measured
throughout the titration, more accurately than with an indicator; at the endpoint
there will be a sudden change in the measured pH.

Conductivity: A measurement of ions in a solution. Ion concentration can change

significantly in a titration, which changes the conductivity. (For instance, during
an acid-base titration, the H+ and OH- ions react to form neutral H2O.) As total
conductance depends on all ions present in the solution and not all ions contribute
equally (due to mobility and ionic strength), predicting the change in conductivity
is more difficult than measuring it.

Color change: In some reactions, the solution changes color without any added
indicator. This is often seen in redox titrations when the different oxidation states
of the product and reactant produce different colors.

Precipitation: If a reaction produces a solid, a precipitate will form during the

titration. A classic example is the reaction between Ag+ and Cl- to form the
insoluble salt AgCl. Cloudy precipitates usually make it difficult to determine the
endpoint precisely.

Isothermal titration calorimeter: An instrument that measures the heat produced

or consumed by the reaction to determine the endpoint. Used in biochemical
titrations, such as the determination of how substrates bind to enzymes.

Thermometric titration: Differentiated from calorimetric titrimetry because the

heat of the reaction (as indicated by temperature rise or fall) is not used to
determine the amount of analyte in the sample solution. Instead, the endpoint is
determined by the rate of temperature change.

Spectroscopy: Used to measure the absorption of light by the solution during

titration if the spectrum of the reactant, titrant or product is known. The
concentration of the material can be determined by Beer’s Law.

Amperometry: Measures the current produced by the titration reaction as a result

of the oxidation or reduction of the analyte. The endpoint is detected as a change
in the current. This method is most useful when the excess titrant can be reduced,
as in the titration of halides with Ag+.

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Stoichiometric Calculations
Units of Concentration

Solutions are homogeneous mixtures containing one or more solutes in a solvent. The
solvent that makes up most of the solution, whereas a solute is the substance that is
dissolved inside the solvent.

Concentrations can be expressed by using percentages. Three different types of

percentage concentrations are used including: mass percent, volume percent and
mass/volume percent.

Mass Percent

The mass percent is used to express the concentration of a solution when the mass
of a solute and the mass of a solution is given.

Mass Percent= (Mass of Solute) / (Mass of Solution) x 100%

Volume Percent

The volume percent is used to express the concentration of a solution when the
volume of a solute and the volume of a solution is given.

Volume Percent= (Volume of Solute) / (Volume of Solution) x 100%

Mass/Volume Percent

The mass/volume percent is used to express the concentration of a solution when the
mass of the solute and volume of the solution is given.

Mass/Volume Percent= (Mass of Solute) / (Volume of Solution) x 100%

The units of the solute and solution should be equivalent.

(2g Solute) / (1kg Solution)

(2g Solute) / (1000g Solution)

(0.002kg Solute) / (1kg Solution)

(5mL Solute) / (1L Solution)

(5mL Solute) / (1000mL Solution)

(0.005L Solute) / (1L Solution)

(8g Solute) / (1L Solution)

(8g Solute) / (1000mL Solution)

(0.008kg Solute) / (1L Solution)

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For Dilute Concentrations

When solutions are too dilute, their percentage concentrations are too low. So, instead
of using really low percentage concentrations such as .00001% or .000000001%,
chemists choose parts per million, parts per billion or parts per trillion to describe a
solution's dilute concentration.

Parts per Million

A concentration of a solution that contained 1g solute and 1000000mL solution (same

as 1mg solute and 1L solution) would create a very small percentage concentration.
Because a solution like this would be so dilute, it would have about the same density
as water (1g/mL).

(1g solute)/(1000000mL solution) x (1mL)/(1g) = (1g solute)/(1000000g solution)

Both the solute and the solution are now expressed in terms of grams: (1g
solute)/(1000000g solution). It could now be said that the solute concentration is 1
part per million (ppm).

1ppm = (1mg Solute) / (1L Solution)

Parts per Billion

Parts per billion (ppb) is almost like ppm, except 1ppb is 1000x more dilute than
1ppm.

1ppb = (1ug Solute) / (1L Solution)

Parts per Trillion

Just like ppb, the idea behind parts per trillion (ppt) is similar to that of ppm.
However, 1ppt is 1000x more dilute than 1ppb and 1000000x more dilute than
1ppm.

1ppt = (1ng Solute) / (1L Solution)

Using Moles
Mole Fraction

The mole fraction of a substance is the fraction of all of its molecules (or atoms) out
of the total number of molecules (or atoms).

XA= (number of moles of substance A) / (total number of moles in solution)

Also, keep in mind that the sum of each of the solution's substances' mole fractions
equals 1.

XA + XB + XC + (all of the other mole fractions in the solution) =1

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Mole Percent

The mole percent (of substance A) is XA in percent form.

Mole percent (of substance A)= XA x 100%

Molarity vs. Molality

While molarity and molality are concentration units that sound a lot alike, they are
completely different from each other.

Molarity

The molarity (M) of a solution is used to represent the amount of moles of solute
per liter of the solution

M= (Moles of Solute) / (Liters of solution)

Molality

The molality (m) of a solution is used to represent the amount of moles of solute per
kilogram of the solvent

m= (Moles of Solute) / (Kilograms of Solvent)

The molarity and molality equations are differ. Volume varies with different
temperatures. Therefore, molarities of solutions also vary at different temperatures.
This creates an advantage for using molality over molarity. Using molalities for lab
experiments would best keep the results within a closer range. Because volume is not
a part of its equation, it makes molality independent of temperature.

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Normality

Normality, N, is similar to molarity, moles of solute per liter of solution. However,

instead of the entire solute, the normality is based on the number of moles of the
active part of the solute, called a chemical equivalent.

For an acid, the chemical equivalent is the number of moles of H+1 ion.

For a base, the chemical equivalent is the number of moles of OH-1 ions.

For an oxidation-reduction solution, the chemical equivalent is the number of moles

of electrons transferred.

The normality of hydrochloric acid, HCl, is the same as the molarity of hydrochloric
acid, because there is one mole of H+1 ions for every one mole of hydrochloric acid.
The normality of sulfuric acid, H2SO4, is twice the molarity because there are two
moles of H+1 ions per mole of sulfuric acid.

nmolequivalents
N 
Lsolution
Formality

Formality, F of a solution may be defined as the number of gram formula masses of

the ionic solute dissolved per litre of the solution. Commonly, the term formality is
used to express the concentration of the ionic solids which do not exist as molecules
but exist as ions.

The purpose of formality is to distinguish the number of moles of a compound from

the number of moles of ions in solutions of ionic compounds or weak electrolytes.

For example 1.0 F solution of Ca(NO3)2 is 2.0 M NO31- or 1.0 M Ca(NO3)2.

n formulaweightunits
F
Lsolution

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 Summary of the Concentration Types
Concentration Mathematical Formula Use
Type

% composition  massA  For ease of making a solution.

mass% A   100
ppm  massA  B  ...  When physical properties are more
 massA  important than chemical properties.
ppm A    10
6
ppb  massA  B  ... 
 massA  Mixtures of solids.
ppb A    10
9

 massA  B  ...  When the concentrations are very low, use

ppm or ppb.

Mole fraction mol1 Mixtures of solids or gases

X1 
mol1  mol 2  ...
Mixtures in which the roles of solute and
solvent are not clear

Molarity nmolSolute Most common laboratory solutions

M
Lsolution

Molality nmolsolute Situations in which the properties of the

m
kgsolvent solvent are studied.

Normality nmolequivalents Acids and bases

N
Lsolution
Oxidizing agents

Reducing agents

Formality n formulaweightunits Ionic compounds

F
Lsolution

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Practice Problems

1- In a solution, there is 111.0mL (110.605g) solvent and 5.24mL (6.0508g)

solute present in a solution. Find the mass percent, volume percent and
mass/volume percent of the solute.

Mass Percent

= (Mass of Solute) / (Mass of Solution) x 100%|

= (6.0508g) / (110.605g + 6.0508g) x 100%

= (.0518688312) x 100% = 5.186883121% Mass Percent= 5.1869%

Volume Percent

= (Volume of Solute) / (Volume of Solution) x 100%

= (5.24mL) / (111.0mL + 5.24mL) x 100%

= (.0450791466) x 100% = 4.507914659% Volume Percent= 4.51%

Mass/Volume Percent

= (Mass of Solute) / (Volume of Solution) x 100%

= (6.0508g) / (111.0mL + 5.24mL) x 100%

= (.0520543703) x 100% = 5.205437027% Mass/Volume Percent= 5.2054%

2) With the solution shown in the picture below, find the mole percent of
substance C.

Moles of C= (5 C molecules) x (1mol C / 6.022x1023 C molecules) = 8.30288941x10-

24
mol C

Total Moles= (24 molecules) x (1mol / 6.022x1023 molecules)= 3.98538691x10-23mol

total

XC= (8.30288941x10-24mol C) / (3.98538691x10-23mol) = .2083333333

Mole Percent of C = XC x 100%

=(.2083333333) x 100% = 20.83333333

Mole Percent of C = 20%

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3) A 1.5L solution is composed of .25g NaCl dissolved in water. Find its molarity.

Moles of NaCl= (.25g) / (22.99g + 35.45g) = .0042778919 mol NaCl

Molarity

= (Moles of Solute) / (Liters of Solution)

= (.0042778919mol NaCl) / (1.5L) = .0028519279M

Molarity= .0029M

4) 0.88g NaCl is dissolved in 2.0L water. Find its molality.

Moles of NaCl = (.88g) / (22.99g + 35.45g) = .0150581793mol NaCl

Mass of water= (2.0L) x (1000mL / 1L) x (1g / 1mL) x (1kg / 1000g) = 2.0kg water

Molality

= (Moles of Solute) / (kg of Solvent)

= (.0150581793mol NaCl) / (2.0kg) = .0075290897m

Molality= .0075m

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Equivalent weight

Equivalent weight is the weight of one equivalent of a given substance which will:

supply or react with one mole of hydrogen cations H+ in an acid-base reaction

supply or react with one mole of electrons e− in a redox reaction

The equivalent weight of a compound can be calculated by dividing the molecular

weight by the number of positive or negative electrical charges that result from the
dissolution of the compound.

The equivalent weight of HCl is 36.5/1 = 36.5

The equivalent weight of H2SO4 is 98/2 = 49
The equivalent weight of NaOH is 40/1 = 40
The equivalent weight of Ca(OH)2 is 74/2 = 37
The equivalent weight of Al2(SO4)3 is 342/6 = 57

Examples:

(1) H2SO4 + 2OH-= 2H2O + SO42-

Molecular weight of sulfuric acid (H2SO4) = 98.07 g/mol

Theoretical Equivalent weight of sulfuric acid (H2SO4) = 49.03 g/equivalent of H+

98.07 g/mol H2SO4 * (1 mole H2SO4 / 2 equivalents of H+) = 49.03 g/equivalent of H+

(2) NH4OH + H+ = H2O + NH4+

Molecular weight of ammonium hydroxide (NH4OH) = 35.00 g/mol

Theoretical Equivalent weight of ammonium hydroxide (NH4OH) = 35.00

g/equivalent of OH-

35.00g/mol of NH4OH * (1 mole NH4OH / 1 equivalent of OH-) = 35.00 g/equivalent

of OH-

(3) H2SO4 + OH-= H2O + HSO4-

Molecular weight of sulfuric acid (H2SO4) = 98.07 g/mol

Theoretical Equivalent weight of sulfuric acid (H2SO4) = 98.07g/equivalent of H+

98.07 g/mol H2SO4 * (1 mole H2SO4 / 1 equivalent of H+) = 98.07g/equivalent of H+

15
Gravimetric analysis
Methods used in Gravimetric Analysis

Precipitation
· Filtration
· Washing
· Drying or ignition
· Weighing

Precipitation Method

Precipitation method is a process of weighing an element in form of precipitates

which is separated by filtration from solution.

Factors affecting on precipitation method:

Precipitates must be free from soluble impurities

· Precipitates must be insoluble in solution
· Precipitates must be readily separated from the solution by filtration
· Precipitates must be convertible into a pure compound by ignition or by simple
evaporation

Example: Gravimetric analysis of a sulphate or halides

Na2SO4 + BaCl2 → BaSO4 + NaCl

NaCl + AgNO3 → AgCl + NaNO3

Mechanism of Precipitation

The reagent used in gravimetric analysis for precipitation is called as precipitating

agent.

When it is added to the solution of the ion under analysis there is an initial induction
period before nucleation occurs. The range of this induction period depends upon the
reagent and reactant.

Induction period is followed by nucleation in which small aggregates or clumps of

atoms form and due to this clumpsis of particles crystals are formed in the filtrate.
Each of these nuclei or aggregates of particles can be composed in just a few atoms.

For example if silver nitrate is slowly reacted with hydrochloric acid, silver chloride
would form and silver ions which are present in excess compared to Cl- ions would
congregate around them.

Ag+ + Cl- AgCl(s)

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With this silver ion, there are some nitrate ions also which further aggregate from the
silver chloride nucleus. They are known as counter ions and have a tendency to
aggregate around the center as these centers have a net positive charge due to the
presence of excess of silver ions and negative charge is required to maintain electrical
neutrality.
Hence the presence of the layer of counter ions around the primary adsorbed ions
forms an electric double layer.

Volatilization gravimetry

The analyte is separated from other constituents of a sample by conversion to a gas of

known chemical composition. The weight of this gas then serves as a measure of the
analyte concentration.

This involves thermal or chemical decomposition of a solid sample. Volatile

components of the reaction can be trapped and weighed. Alternatively, weighing of
the residue is carried out.

Thermogravimetry is one form of volatilization gravimetry. Here, the sample’s mass

is continuously monitored as temperature is increased. A thermogram can be obtained
to be used in calculation. The products of any decomposition reaction must be known
when performing volatilization gravimetry.

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Volatilization gravimetry is employed in analysis of organic compounds to determine
C and H. The organic compound is burnt in oxygen, carbon dioxide and water are
trapped and their masses determined. From this data C and H can be determined.

Carbonate can also be determined by volatilization gravimetry. The carbonate is

decomposed by dilute acid and analysis proceeds by either the direct or indirect
method.

Direct method - CO2 produced is absorbed and its mass determined by weighing.

Indirect method – Loss of mass of sample is determined and this loss is taken to be
mass of CO2 produced.

The indirect method gives more accurate results.

Gravimetric factor
General form for calculations

The gravimetric factor (GF) comes from a combination of the mole ratios and the
formula weights used in the stoichiometric calculation.

For example, if you were looking for SO3 and your precipitate was BaSO4, the
gravimetric factor would be:

The numbers, 80.064 and 233.391, are the formula weights of SO3 and BaSO4,
respectively.

The main question is how to determine the mole ratio without knowing the entire
reaction. This is actually quite easy. Simply balance the common element. Most of
the time oxygen is not considered. In the above example, sulfur appears in both
terms.

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There is only one sulfur in each term and the sulfurs are balanced. In other words, the
mole ratio is 1.

Consider the following GF:

The common element is silver, Ag.

However, there are two silver atoms represented in the upper term and only one in the
lower term.

To "balance" the silver atoms, a 2 is placed in front of the substance in the lower term.

The calculation set-up for this gravimetric factor would be:

Example: How many pounds of zinc must react with hydrochloric acid to produce
1080 pounds of zinc chloride?

The first step would be to write or look up the balanced chemical equation for Zn
reactiong with HCl to form zinc Chloride:

Zn + 2 HCl → ZnCl2 + H2

1 mole of Zn to 2 moles of HCl, makes 1 mole of ZnCl2 and 1 mole of H2.

How many moles of ZnCl2 is contained in 1080 pounds of ZnCl2.

The formula mass of ZnCl2 has

65.405 g/mol + 2 (35.453 g/mol) = 136.311 g/ mol of ZnCl2.

1 Pound = 453.59237 Grams.

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(136.311 g/mol ZnCl2) X (1 lb / 453.59237 g) = .3005 lbs/mol ZnCl2
we want to make 1080lbs. How many moles is that?

1080 lbs ZnCl2 X ( 1 mol ZnCl2/ .3005 lbs) = 3594.0010 moles ZnCl2

Each mole of Zn make 1 mole of ZnCl2

Since it is a 1 to 1 ratio, to get 3594.0010 moles of ZnCl2 for our product, we must put
in exactly 3594.0010 moles of Zn

Convert from moles to pounds for Zn. (Zn has a mass of 65.409 g/mol).
(3594.0010 moles of Zn) X (65.409 g/mol) = 235,080.0114 g of Zn

To convert from grams to pounds

(235,080.0114 g of Zn) X (1 lb / 453.59237 g) = 518.2627 lbs Zn needed to yield

1080 lbs of ZnCl2

Example:

A certain barium halide exists as the hydrated salt BaX2.2H2O, where X is the
halogen. The barium content of the salt can be determined by gravimetric methods. A
sample of the halide (0.2650 g) was dissolved in water (200 cm3) and excess sulfuric
acid added. The mixture was then heated and held at boiling for 45 minutes. The
precipitate (barium sulfate) was filtered off, washed and dried. Mass of precipitate
obtained = 0.2533 g. Determine the identity of X.

Answer:

The precipitate is barium sulfate. The first stage is to determine the number of moles
of barium sulfate produced, this will, in turn give us the number of moles of barium in
the original sample.

Relative Molecular Mass of barium sulfate

= 137.34 (Ba) + 32.06 (S) + (4 x 16.00) (4 x O) = 233.40

Number of moles
= mass / RMM = 0.2533 / 233.40 = 1.09 x 10 -3

This is the number of moles of barium present in the precipitate and, therefore, the
number of moles of barium in the original sample. Given the formula of the halide,
(i.e. it contains one barium per formula unit), this must also be the number of moles of
the halide. From this information we can deduce the relative molecular mass of the
original halide salt:

RMM = mass / number of moles

= 0.2650 / 1.09 x 10-3 = 244.18

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The relative atomic mass of 2 X will be given by the RMM of the whole salt - that of
the remaining components; So RAM of 2 X = 244.18 - 173.37 = 70.81

2 X = 70.81, so X = 35.41.

The RAM of chlorine is 35.45 which is in good agreement with the result obtained
and hence the halide salt is hydrated barium chloride and X = Chlorine

Problems

1. A sample (0.203 g) of hydrated magnesium chloride (MgClm.nH2O) was dissolved

in water and titrated with silver nitrate solution (0.100 mol dm-3), 20.0 cm3 being
required. Another sample of the hydrated chloride lost 53.2 % of its mass when heated
in a stream of hydrogen chloride, leaving a residue of anhydrous magnesium chloride.
Calculate the values of m and n. (Answer: m = 2, n = 6)

2. When an sample of impure potassium chloride (0.4500g) was dissolved in water

and treated with an excess of silver nitrate, 0.8402 g of silver chloride was
precipitated. Calculate the percentage KCl in the original sample. (Answer: 97.12 %)

Chemical Equilibrium
In pure water (H2O), there are an equal number of hydrogen ions (H+) and hydroxyl
ions(OH−). The solution is neither acidic nor basic.

Some of the water molecules lose hydrogen and become hydroxyl ions

The "lost" hydrogen ions join up with water molecules to form hydronium ions
(H3O+). For simplicity, hydronium ions are referred to as hydrogen ions H+.

H+ + H2O H3O+

An acid is a substance that donates hydrogen ions.

A base is a substance that accepts hydrogen ions.

Acidity and alkalinity are measured with a logarithmic scale called pH.

pH = −log [H+]

The pH scale ranges from 0 to 14

The square brackets around the H+ mean "concentration".

Pure water has a neutral pH of 7.

pH values lower than 7 are acidic, and pH values higher than 7 are alkaline
(basic).

21
Equilibrium Constant
For a general chemical equilibrium

the equilibrium constant can be defined such that, at equilibrium

Kc - equilibrium constant

For ideal behavior this quotient has a value of 1

Water-dissociation equilibrium constant (Kw)

The product of the equilibrium concentration of the H3O+ and OH- ions in an aqueous
solution:

Kw = 1.0 X 10-14 at 25C

Acid-Ionization Constant Ka

Ka - acid dissociation constant (acid-ionization constant) is a quantitative measure

of the strength of an acid in solution

where : HA − the acid that dissociates by splitting into A−

A− − the conjugate base of the acid

H+ − the hydrogen ions or proton ( in aqueous solutions exists as the hydronium ion)

The chemical species HA, A− and H+ are said to be in equilibrium when their
concentrations do not change with the passing of time

Ka − is written as a quotient of the equilibrium concentrations (in mol/L), denoted by

[HA], [A−] and [H+]

The larger the value of pKa = the weaker the acid

22
Base-Ionization constant Kb

A measure of the relative strength of a base

For the generic base dissociation reaction with water

The base-ionization equilibrium constant is the mathematical product of the

equilibrium concentrations of the products of this reaction divided by the equilibrium
concentration of the original base

Kb is the product of the concentrations of the products over the concentration of the
reactants (not including water):

Water is not included in the base-ionization equilibrium expression because the [H2O]
has no effect on the equilibrium.

As the Kb value of an base increases, the strength of the base increases

strong base: Kb > 1

weak base: Kb < 1

Relationship between Ka, Kb and Kw

Ka and Kb can be found if the other is known.

Compounds with large Ka values will have small Kb values because strong acids are
extremely weak bases.

Compounds with large Kb values have small Ka values because strong bases are
extremely weak acids.

Example Equilibrium Calculations

Calculate the pH of a 0.10 M NH3 solution. (Kb = 1.8 x 10-5)

begin by setting up the reaction •

Note that there is a forward/backward arrow, indicating that the base ionizes only
slightly since this is a weak base

Next set up the concentration chart with the initial and equilibrium concentrations
of the base and its ions:

23
 [NH3] [NH4+] [OH-]

Initial 0.01 0 0

Equilibrium 0.01 - Δ Δ Δ

Write the base ionization equilibrium expression (Kb):

Substitution in the values for the Kb expression:

Assume that is negligible when subtracted from the initial concentration of the
base:

Solve for Δ

Check the assumption to make sure that less than 5% of the base actually ionizes.

Since less than 5% of the base ionized in water, our assumption was valid.

So according to our chart, = [OH-]. The problem, however, asks for the pH of the
solution, so we must eventually arrive at a pH value. There are two ways to get to
this answer. One way is to convert the [OH-] to [H3O+] by using the following
equation:

24
Another way to find the pH is to find the pOH first and then convert to pH from
there:

Either way, we ultimately arrive at the same answer.

Calculate the pH of a 0.030 M NaC6H5O2 solution. (Ka = 6.3 x 10-5 for

HC6H5O2).

First, let's begin by writing the reaction for the dissociation of the acid salt in
water, noting the concentrations of the ions formed:

Since the mole ratio of the acid salt to its respective ions is 1:1, the acid salt
dissociates to give equimolar amounts of each ion equal to the concentration of
the acid salt.

25
The anion formed in the above reaction can act as a H+ acceptor (base) in
water. We can write the reaction for the ionization of this base in water:

Set up a chart with the concentrations of the base and the ions it forms in the
reaction with water

Write the Kb expression:

The next step would be to substitute the given Kb value and the values from the
chart into the Kb expression.

We can use the relationship between Ka, Kb, and Kw to calculate Kb:

Now we can substitute the values into the Kb expression:

Assume that Δ is negligible when subtracted from the initial concentration of the
base:

Solve for Δ

26
Check to make sure that the assumption was valid

Since less than 5% of the initial base concentration ionized, our assumption was
valid.

According to our chart, = [OH-]. However, we were asked to find pH so we must

eventually arrive at a pH value:

Monoprotic acid and Basese

Monoprotic acids are acids that can release only one proton per molecule and
have one equivalence point.

Here is a table of some common monoprotic acids:

Name Formula Ka

Hydrochloric acid (strong) HCl 1.3 x 106

Nitric acid (strong) HNO3 2.4 x 101

Acetic acid (weak) CH3COOH 1.74 x 10-5

27
 Monoprotic Bases are bases that can only react with one proton per molecule and
similar to monoprotic acids, only have one equivalence point.

Here is a list of some common monoprotic bases:

Name Formula Ka

Sodium hydroxide (strong) NaOH 6.3 X 10-1

Potassium hydroxide
KOH 3.16 X 10-1
(strong)

Ammonia (weak) NH3 1.80 x 10-5

Example 1: What is the pH of the solution that results from the addition of 200
mL of 0.1 M CsOH(aq) to 50 mL of 0.2M HNO2(aq)? (pKa= 3.14 for HNO2)

Polyprotic Acids and Basese

Polyprotic acids are acids that can lose several protons per molecule. They can be
further categorized into diprotic acids and triprotic acids, those which can donate
two and three protons. Here is a list of some common polyprotic acids:

Name Formula Ka 1 Ka 2 Ka 3

Sulfuric acid (strong,

H2SO4 1.0 x 103 1.2 x 10-2 ---
diprotic)

Carbonic acid (weak,

H2CO3 4.2 x 10-7 4.8 x 10-11 ---
diprotic)

Phosphoric acid (weak, 4.2 x

H3PO4 7.1 x 10-3 6.3 x 10-8
triprotic) 10-13

Polyprotic bases are bases that can attach several protons per molecule. Similar to
polyprotic acids, polyprotic bases can be categorized into diprotic bases and
triprotic bases. Here is a list of some common polyprotic bases:

Example 2: For a 4.0 M H3PO4 solution, calculate (a) [H3O+] (b) [HPO42--] and
(c) [PO43-].

28
Example 3.

The polyprotic acid H2SO4 can ionize two times (Ka1 >> 1 , Ka2 = 1.1 x 10 -2 )If
we start with 9.50*10-3 M solution of H2SO4, what are the final concentrations of
H2SO4, HSO4-, SO42-, and H30+.

H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq) Ka1 = 1 x 103

HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq) Ka2 = 1.2 x 10-2

Answer
The equation for the first ionization is
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)
This equation goes to completion because H2SO4 is a strong acid and Ka1 >> 1
So since the reaction goes to completion, doing an ICE Table you get
[H30+] = 9.50 * 10-3 M and [HSO4-] = 9.50 * 10-3 M (after the first ionization).
The equation of the second ionization is
HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)

Using the equation

[𝐻3 𝑂][𝑆𝑂4 2− ]
𝐾𝑎2 = , Ka2 = 1.1 x 10 -2
[𝐻𝑆𝑂4 − ]
and an ICE Table to get

x + 0.0205x – 0.0001045 = 0.
2

Then you use the quadratic equation to solve for X, to get x = 0.004226.
Now we need to solve for the necessary concentrations
[H2SO4] = 0 (because the first ionization reaction went to completion)
[HSO 4 ̶] = Ka1 ̶ Ka2 = 9.50*10-3 M - 0.004226 M = 5.27*10-3 M
[SO4 ]̶ = Ka2 = .004226 M
[H3O+] = Ka1 + Ka2 = 9.50*10-3 M + 0.004226 M = 1.37*10-2 M

29
 57
Hydrogen sulfide H2S is a weak acid that dissociates in steps. Some of the H2S
molecules lose a proton in the first step to form the HS-, or hydrogen sulfide ion.

First step:

H2S(aq) + H2O(l) H3O+(aq) + HS-(aq)

A small fraction of the HS- ions formed in this reaction then go on to lose another
H+ ion in a second step.

Second step:

HS-(aq) + H2O(l) H3O+(aq) + S2-(aq)

Since there are two steps in this reaction, we can write two equilibrium constant
expressions.

30
There are four unknowns [H3O+], [H2S], [HS-], and [S2-] because the [H3O+] and
[HS-] terms appear in both equations.

Four equations are needed to solve for four unknowns.

two equations are presented: the Ka1 and Ka2 expressions.

Ka1 for this acid is almost a million times larger than the value of Ka2.

Ka1 >> Ka2

This means that only a small fraction of the HS- ions formed in the first step go on
to dissociate in the second step

Most of the H3O+ ions in this solution come from the dissociation of H2S

Most of the HS- ions formed in this reaction PSS remain in solution

First assumption: [H3O+] ≈ [HS-]

H2S is a weak acid (Ka1 = 1.0 x 10-7, Ka2 = 1.3 x 10-13).

most of the H2S that dissolves in water will still be present when the solution
reaches equilibrium.

The equilibrium concentration of H2S is approximately equal to the initial

concentration.

Second assumption: [H2S] ≈ CH2S

Four equations of four unknowns are ready to be calculated the H3O+, H2S, HS-,
and S2- concentrations at equilibrium in a saturated solution of H2S in water

31
[H3O+] ≈ [HS-]

[H2S] ≈ CH2S

Because Ka1 is so much larger than Ka2 for this acid

We then invoke one of our assumptions.

[H2S] ≈ CH2S ≈ 0.10 M

Substituting this approximation into the Ka1 expression gives the following
equation.

We then invoke the other assumption [H3O+] ≈ [HS-] ≈ C

Substituting this approximation into the Ka1 expression gives the following result.

We now solve this approximate equation for ΔC.

ΔC ≈ 1.0 x 10-4

We know the H2S, H3O+, and HS- concentrations.

[H2S] ≈ 0.10 M

[H3O+] ≈ [HS-] ≈ 1.0 x 10-4 M

Having extracted the values of three unknowns from the first equilibrium
expression, we turn to the second equilibrium expression.

Because the equilibrium concentrations of the H3O+ and HS- ions are more or less
the same, the S2- ion concentration at equilibrium is approximately equal to the
value of Ka2 for this acid. [S2-] ≈ 1.3 x 10-13 M

32
The dissociation of H2S is small compared with the initial concentration

The HS- and H3O+ ion concentrations obtained from this calculation are 1.0 x 10-4
M, which is 0.1% of the initial concentration of H2S.

The following assumption is valid.

[H2S] ≈ ΔCH2S ≈ 0.10 M

The difference between the S2- and HS- ion concentrations are large enough to
allow to assume that all of the H3O+ ions at equilibrium are formed in the first step
and that all of the HS- ions formed in this step remain in solution.

The S2- ion concentration obtained from this calculation is 109 times smaller than
the HS- ion concentration.

Thus, our other assumption is also valid.

[H3O+] ≈ [HS-]

We can therefore summarize the concentrations of the various components of this

equilibrium as follows.

[H2S] ≈ 0.10 M

[H3O+] ≈ [HS-] ≈ 1.0 x 10-4 M

[S2-] ≈ 1.3 x 10-13 M

33
Examples:
Na2CO3(aq) 2 Na+(aq) + CO32-(aq)
CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq) Kb1 = ?
HCO3-(aq) + H2O(l) H2CO3(aq) + OH-(aq) Kb2 = ?

Ka1Kb2 = Kw

Ka2Kb1 = Kw

34
 [OH-] [HCO3-] C

[CO32-] CNa2CO3

C 0.0046 M

[CO32-] = 0.10 - C 0.095 M

[OH-] [HCO3-] C 0.0046 M

[H2CO3] 2.2 x 10-8 M

[CO32-] 0.095 M

[OH-] [HCO3-] 4.6 x 10-3 M

[H2CO3] 2.2 x 10-8 M

Triprotic Acids

calculate the H3O+, H3PO4, H2PO4-, HPO42-, and PO43- concentrations

at equilibrium in a 0.10 M H3PO4 solution, for which Ka1 = 7.1 x 10-
3, K
a2 = 6.3 x 10 , and Ka3 = 4.2 x 10
-8 -13.

assume that this acid dissociates by steps and analyze the first step
the most extensive reaction.

35
 [H3O+] [H2PO4-] C

C = 0.023 M

[H3PO4] 0.10 - C 0.077 M

[H3O+] [H2PO4-] 0.023 M

[HPO42-] 6.3 x 10-8

[PO43-] 1.2 x 10-18 M

[H3PO4] 0.077 M

[H3O+] [H2PO4-] 0.023 M

[HPO42-] 6.3 x 10-8 M

[PO43-] 1.2 x 10-18 M

Practice Problem 7:

Calculate the H3O+, H3Cit, H2Cit-, HCit2-, and Cit3- concentrations in an 1.00 M solution
of citric acid. (H3Cit: Ka1 = 7.5 x 10-4, Ka2 = 1.7 x 10-5, Ka3 = 4.0 x 10-7)

36
Electrolyte
An electrolyte is a compound that ionizes when dissolved in suitable ionizing
solvents such as water. This includes most soluble salts, acids, and bases.

The individual components of the electrolyte dissociate due to the thermodynamic

interactions between solvent and solute molecules, in a process called solvation.

For example, when (sodium chloride), NaCl, is placed in water, the salt dissolves into
its component ions, according to the dissociation reaction

NaCl(s) → Na+(aq) + Cl−(aq)

It is also possible for substances to react with water producing ions, e.g., carbon
dioxide gas dissolves in water to produce a solution which contains hydronium,
carbonate, and hydrogen carbonate ions.

An electrolyte in a solution may be described as concentrated if it has a high

concentration of ions, or dilute if it has a low concentration. If a high proportion of the
solute dissociates to form free ions, the electrolyte is strong; if most of the solute does
not dissociate, the electrolyte is weak.

Stability Constants of Complexes

Stability constant is equilibrium constant for the formation of a complex in
solution. It is a measure of the strength of the interaction between the reagents that
come together to form the complex. There are two main kinds of complex:
compounds formed by the interaction of a metal ion with a ligand and
supramolecular complexes, such as host-guest complexes and complexes of
anions. The stability constant(s) provide the information required to calculate the
concentration(s) of the complex(es) in solution

M = metal ion

L = ligand

The number of water molecules attached to each metal ion is constant. In dilute
solutions the concentration of water is effectively constant. The expression
becomes

37
 For the general equilibrium

Solubility Product Constants, Ksp

Solubility product constants are used to describe saturated solutions of ionic

compounds of relatively low solubility.

MxAy(s) --> x My+(aq) + y Ax-(aq)

The general equilibrium constant for such processes can be written as:

Ksp = [My+]x[Ax-]y

Example: Calculate the solubility product constant for lead(II) chloride, if 50.0
mL of a saturated solution of lead(II) chloride was found to contain 0.2207 g of
lead(II) chloride dissolved in it.

PbCl2(s) --> Pb2+(aq) + 2 Cl-(aq) Ksp = [Pb2+][Cl-]2

Convert the amount of dissolved lead(II) chloride into moles per liter

(0.2207 g PbCl2)(1/50.0 mL solution)(1000 mL/1 L)(1 mol PbCl2/278.1 g PbCl2)

= 0.0159 M PbCl2

PbCl2 (s) Pb2+(aq) Cl-(aq)

Initial Concentration All solid 0 0

Change in Concentration - 0.0159 M (dissolves) + 0.0159 M + 0.0318 M

Equilibrium
Less solid 0.0159 M 0.0318 M
Concentration

Ksp = [0.0159][0.0318]2 = 1.61 x 10-5

38
Strong acid
A strong acid is one which is virtually 100% ionised in solution.

These reactions are one-way reactions. The acid is virtually 100%

ionised.

Other common strong acids include sulphuric acid and nitric acid.

You may find the equation for the ionisation written in a simplified
form:

Strong acids and pH

pH is a measure of the concentration of hydrogen ions in a solution.

The lower the pH, the higher the concentration of hydrogen ions in the
solution.

Defining pH

Calculate the pH of 0.1 mol dm-3 hydrochloric acid.

log10 [0.1] = -1

But pH = - log10 [0.1]

- (-1) = 1

pH = 1.

39
Strong bases
A strong base like sodium hydroxide or potassium hydroxide is the
base that fully ionize means the compound that being 100% split up
into metal ions and hydroxide ions in solution.

An outline of the method of working out the pH of a strong base

 Work out the concentration of the hydroxide ions.

 Use Kw to work out the hydrogen ion concentration.
 Convert the hydrogen ion concentration to a pH.

pH = - log [H+]

-
pOH = - log [OH ]

An example To find the pH of 0.500 mol dm-3 sodium hydroxide

solution:

Because the sodium hydroxide is fully ionic, each mole of it gives that
same number of moles of hydroxide ions in solution.

[OH-] = 0.500 mol dm-3

Kw = 1.00 x 10-14 mol2 dm-6.

[H+] [OH-] = 1.00 x 10-14

[H+] x 0.500 = 1.00 x 10-14

pH =13.7.

40
Weak acids
A weak acid is one which doesn't ionise fully when it is dissolved in
water.

Most organic acids are weak. Hydrogen fluoride (dissolving in water to

produce hydrofluoric acid) is a weak inorganic acid

If the acid is weak the concentration of the water is constant.

For example,

An introduction to pKa

acid Ka (mol dm-3) pKa

hydrofluoric acid 5.6 x 10-4 3.3

methanoic acid 1.6 x 10-4 3.8

ethanoic acid 1.7 x 10-5 4.8

hydrogen sulphide 8.9 x 10-8 7.1

41
Weak bases
A weak base is one which doesn't convert fully into hydroxide ions in
solution.

Ammonia is a typical weak base. Ammonia itself obviously doesn't

contain hydroxide ions, but it reacts with water to produce ammonium
ions and hydroxide ions.

The reaction is reversible.

Comparing the strengths of weak bases in solution: Kb

When a weak base reacts with water, the position of equilibrium varies
from base to base. The further to the left it is, the weaker the base.

In this case the equilibrium constant is called Kb. This is defined as:

The table shows some values for Kb and pKb for some weak bases.

base Kb (mol dm-3) pKb

C6H5NH2 4.17 x 10-10 9.38

NH3 1.78 x 10-5 4.75

CH3NH2 4.37 x 10-4 3.36

CH3CH2NH2 5.37 x 10-4 3.27

As Kb gets bigger, pKb gets smaller. The lower the value of pKb, the
stronger the base.

42
THEORIES OF ACIDS AND BASES
The Arrhenius Theory of acids and bases
 Acids are substances which produce hydrogen ions in solution.
 Bases are substances which produce hydroxide ions in solution.

Neutralisation happens because hydrogen ions and hydroxide ions

react to produce water.

Limitations of the theory

Hydrochloric acid is neutralised by both sodium hydroxide solution

and ammonia solution. In both cases, a white salt can be produced.

In the sodium hydroxide case, hydrogen ions from the acid are reacting
with hydroxide ions from the sodium hydroxide - in line with the
Arrhenius theory.

However, in the ammonia case, there don't appear to be any hydroxide

ions!

The ammonia reacts with the water to produce ammonium ions and
hydroxide ions:

This is a reversible reaction, and in a typical dilute ammonia solution,

about 99% of the ammonia remains as ammonia molecules.
Nevertheless, there are hydroxide ions there, and we can squeeze this
into the Arrhenius theory.

However, this same reaction also happens between ammonia gas and
hydrogen chloride gas.

Here, there aren't any hydrogen ions or hydroxide ions in solution. The
Arrhenius theory wouldn't count this as an acid-base reaction.

The Bronsted-Lowry Theory of acids and bases

43
  An acid is a proton (hydrogen ion) donor.
 A base is a proton (hydrogen ion) acceptor.

When an acid in solution reacts with a base, the hydroxonium ion is

functioning as the acid.

For example, a proton is transferred from a hydroxonium ion to a

hydroxide ion to make water.

The hydrogen chloride / ammonia problem

If it is in solution, the ammonia accepts a proton from a hydroxonium

ion:

If the reaction is happening in the gas state, the ammonia accepts a

proton directly from the hydrogen chloride:

44
Either way, the ammonia acts as a base by accepting a hydrogen ion
from an acid.

Conjugate pairs

When hydrogen chloride dissolves in water, almost 100% of it reacts

with the water to produce hydroxonium ions and chloride ions.
Hydrogen chloride is a strong acid, and we tend to write this as a one-
way reaction:

In fact, the reaction between HCl and water is reversible.

For the forward reaction:

 The HA is an acid because it is donating a proton (hydrogen

ion) to the water.
 The water is a base because it is accepting a proton from the
HA.

For the back reaction between the hydroxonium ion and the A- ion:

 The H3O+ is an acid because it is donating a proton (hydrogen

ion) to the A- ion.
 The A- ion is a base because it is accepting a proton from the
H3O+.

The reversible reaction contains two acids and two bases. We think of
them in pairs, called conjugate pairs.

For the conjugated pairs HA and A- , A- is the conjugated base of the

acid HA and for the pair of the water and the hydroxonium ion, the
hydroxonium ion is the conjugated acid of base water.

A second example of conjugate pairs

45
This is the reaction between ammonia and water :

Ammonia is a base because it is accepting hydrogen ions from the

water. The ammonium ion is its conjugate acid - it can release that
hydrogen ion again to reform the ammonia.

The water is acting as an acid, and its conjugate base is the hydroxide
ion. The hydroxide ion can accept a hydrogen ion to reform the water.

Looking at it from the other side, the ammonium ion is an acid, and
ammonia is its conjugate base. The hydroxide ion is a base and water is
its conjugate acid.

Amphoteric substances
A substance which can act as either an acid or a base is described as
being amphoteric.

Water may act as a base and in other reactions it may act as an acid.

The Lewis Theory of acids and bases

 An acid is an electron pair acceptor.
 A base is an electron pair donor.

The relationship between the Lewis theory and the Bronsted-

Lowry theory

Lewis bases

46
The Bronsted-Lowry theory says that they are acting as bases because
they are combining with hydrogen ions. The reason they are combining
with hydrogen ions is that they have lone pairs of electrons - which is
what the Lewis theory says. The two are entirely consistent.

On the Lewis theory, any reaction in which the ammonia or water used
their lone pairs of electrons to form a co-ordinate bond would be
counted as them acting as a base.

Ammonia reacts with BF3 by using its lone pair to form a co-ordinate
bond with the empty orbital on the boron.

47
Lewis acids

Lewis acids are electron pair acceptors.

In the above example, the BF3 is acting as the Lewis acid by accepting
the nitrogen's lone pair. On the Bronsted-Lowry theory, the BF3 has
nothing acidic about it.

The reaction between ammonia and hydrogen chloride gas?

The ammonia is donating its lone pair to a hydrogen ion - a simple

proton with no electrons around it.

Chlorine is more electronegative than hydrogen, and that means that

the hydrogen chloride will be a polar molecule. The electrons in the
hydrogen-chlorine bond will be attracted towards the chlorine end,
leaving the hydrogen slightly positive and the chlorine slightly
negative.

The lone pair on the nitrogen of an ammonia molecule is attracted to

the slightly positive hydrogen atom in the HCl. As it approaches it, the
electrons in the hydrogen-chlorine bond are repelled still further
towards the chlorine.

Eventually, a co-ordinate bond is formed between the nitrogen and the

hydrogen, and the chlorine breaks away as a chloride ion.

The whole HCl molecule is acting as a Lewis acid. It is accepting a

pair of electrons from the ammonia, and in the process it breaks up.
Lewis acids don't necessarily have to have an existing empty orbital

48
Solubility Rules
Solubility is a physical property of a pure substance. For stirring a 10 gram pure solid
compound into 100 g of water. One of three things can happen (assuming the
compound doesn't react with water):

1) The solid is soluble in water if the entire solid dissolves quickly and easily.
2) The compound is moderately or slightly soluble, if some of the solid
dissolves; depending on how much of the original 10 g appears to dissolve.
3) The compound is insoluble in water if none of the solid dissolves.

Recrystallization

Solubility is dependent on temperature. The solubility of most, but not all, salts
increases as the temperature increases. Imagine dissolving as much of a salt as
possible in hot water, and then allowing the solution to cool. A solution that contains
the maximum amount of a dissolved solute is said to be saturated. As it cools, the
solution can no longer hold as much salt, so the excess amount separates as a solid. If
the solution is cooled slowly enough the solid separates as crystals. The process of
recrystallization is used to purify substances, because the ordered arrangement of
ions in the crystal lattice disfavors the inclusion of impurities which might have been
present in the original solid. The impurities stay in solution when the crystals are
collected by filtration.

Precipitation Reactions
If solutions of two different salts are mixed, then there may be two different cations
and two different anions in the solution. If one combination of cation and anion
corresponds to an insoluble salt, then this salt will precipitate (separate as a solid) as
soon as the original solutions are mixed. We can represent such a chemical reaction
using ionic equations just as we did for neutralization reactions.

For example a solution of lithium bromide mixed with silver nitrate.

...(1)
LiBr (s) Li+ (aq) + Br- (aq)
...(2)
AgNO3 (s) Ag+ (aq) + NO3- (aq)

Li+ (aq) + Br- (aq) + Ag+ (aq) Li+ (aq) + NO3- ...(3)
+ NO3- (aq) (aq) + AgBr (s)
...(4)
Ag+ (aq) + Br- (aq) AgBr (s)
...(5)
LiBr (aq) + AgNO3 (aq) LiNO3 (aq) + AgBr (s)

49
Another example of a balanced equation for the reaction of potassium phosphate
with magnesium chloride.

K3PO4 (aq) + MgCl2 unbalanced

Mg3(PO4)2 (s) + KCl (aq)
(aq)

2 K3PO4 (aq) + 3 MgCl2 Mg3(PO4)2 (s) + 6 balanced

(aq) KCl (aq)

Solubility equilibrium
Solubility equilibrium exists when a chemical compound in the solid state is in chemical
equation with a solution of that compound
Solubility equilibria are important in pharmaceutical, environmental and many other scenarios.
The equilibrium is an example of dynamic equilibrium in that some individual molecules
migrate between the solid and solution phases such that the rates of dissolution and precipitate
are equal to one another.

The concentration of the solute in a saturated solution is known as the solubility.

Units of solubility may be molar (mol dm−3) or expressed as mass per unit volume, as μg ml−1.
A solution containing a higher concentration of solute than the solubility is said to be
supersaturated.

The equilibrium constant can be specified as activities.

The equilibrium constant is usually divided by the activity coefficients, to become a quotient of
concentrations.

Solubility is temperature dependent.

In accordance with Le Chatelier's Principle:
- When the dissolution process is endothermic (heat is absorbed), solubility increases
with rising temperature.
- When the process is exothermic (heat is released) solubility decreases with rising
temperature.
The temperature effect is the basis for the process of recrystalization, which can be used to
purify a chemical compound.

Ionic compounds normally dissociate into their constituent ions when they dissolve in water.
For example:

where
- K is the thermodynamic equilibrium constant
- braces indicate activity.

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The activity of a pure solid = 1
When the solubility of the salt is very low, the activity coefficients of the ions in solution are
nearly = 1

The solubility product for a general compound ApBq is given by:

ApBq pAq+ + qBp-

Ksp = [A]p[B]q
When the product dissociates the concentration of B = q/p times the concentration of A.

[B] = q/p [A]

Ksp = [A]p (q/p)q [A]q

=(q/p)q × [A]p+q

Ksp = 4.93×10−5, log Ksp = -4.32.

The smaller the value, or the more negative the log value, the lower the solubility.

Some salts are not fully dissociated in solution.

For hydroxides solubility products are often given in a modified form, K*sp
using hydrogen ion concentration in place of hydroxide ion concentration.

Kw=[H+][OH-]

Ca(OH)2 Ca2+ + 2 OH-

Ksp = [Ca2+][OH-]2 = [Ca2+]Kw2[H+]-2
K*sp = Ksp/Kw2 = [Ca2+][H+]-2
log Ksp for Ca(OH)2 is about -5 at ambient temperatures;
log K*sp = -5 + 2 × 14 = 23

Example; the solubility of AgCl, is lowered when sodium chloride is added to a suspension of
AgCl in water.

AgCl(s) Ag+(aq) + Cl-(aq);

Ksp = [Ag+][Cl-]

The solubility, S, in the absence of a common ion can be calculated as follows.

Let the concentration of [Ag+](aq) = x
Ksp = x2;

S=x=

Ksp for AgCl = 1.77×10−10 mol2dm−6 at 25 °C

The solubility = 1.33×10−5 mol dm−3

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Now suppose that sodium chloride is also present, at a concentration of 0.01 mol dm−3.
The solubility, ignoring any possible effect of the sodium ions, is now calculated by:

Ksp = x(0.01 + x)

x2 + 0.01 x - Ksp = 0

In the case of silver chloride x2 is very much smaller than 0.01 x

S = x = Ksp / 0.01 = 1.77×10−8 mol dm-3

Definitions of oxidation and reduction (redox)

Oxidation and reduction in terms of oxygen transfer

Definitions

 Oxidation is gain of oxygen.

 Reduction is loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are going on side-by-side, this is known as a
redox reaction.

Oxidising and reducing agents

An oxidising agent is substance which oxidises something else. In the above example,
the iron(III) oxide is the oxidising agent.

A reducing agent reduces something else. In the equation, the carbon monoxide is the
reducing agent.

 Oxidising agents give oxygen to another substance.

 Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of hydrogen transfer

These are old definitions which aren't used very much nowadays. The most likely
place you will come across them is in organic chemistry.

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Definitions

 Oxidation is loss of hydrogen.

 Reduction is gain of hydrogen.

Notice that these are exactly the opposite of the oxygen definitions.

For example, ethanol can be oxidised to ethanal:

You would need to use an oxidising agent to remove the hydrogen from the ethanol.
A commonly used oxidising agent is potassium dichromate(VI) solution acidified
with dilute sulphuric acid.

Ethanal can also be reduced back to ethanol again by adding hydrogen to it. A
possible reducing agent is sodium tetrahydridoborate, NaBH4.

An update on oxidising and reducing agents

 Oxidising agents give oxygen to another substance or remove hydrogen from

it.
 Reducing agents remove oxygen from another substance or give hydrogen to
it.

Oxidation and reduction in terms of electron transfer

Definitions

 Oxidation is loss of electrons.

 Reduction is gain of electrons.

A simple example

The equation shows a simple redox reaction which can obviously be described in
terms of oxygen transfer.

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 A last comment on oxidising and reducing agents

The magnesium is reducing the copper(II) ions by giving them electrons to neutralise
the charge. Magnesium is a reducing agent.

Tthe copper(II) ions are removing electrons from the magnesium to create the
magnesium ions. The copper(II) ions are acting as an oxidising agent.

 An oxidising agent oxidises something else.

 Oxidation is loss of electrons.
 An oxidising agent takes electrons from that other substance.
 Oxidising agent must gain electrons.

An introduction to redox quilibria and electrode potential

The differing reactivities of metals

When metals react, they give away electrons and form positive ions. for example,
Mg (aq) or Cu2+(aq).
2+

to compare the ease with which these two changes take place:

The first reaction happens much more readily than the second one because
magnesium is more reactive than copper.

Looking at this from an equilibrium point of view

Suppose you have a piece of magnesium in a beaker of water. There will be some
tendency for the magnesium atoms to shed electrons and go into solution as magnesium
ions. The electrons will be left behind on the magnesium.

54
 In a very short time, there will be a build-up of electrons on the magnesium, and it
will be surrounded in the solution by a layer of positive ions. These will tend to stay close
because they are attracted to the negative charge on the piece of metal.

Some of them will be attracted enough that they will reclaim their electrons and stick
back on to the piece of metal.

A dynamic equilibrium will be established when the rate at which ions are leaving the
surface is exactly equal to the rate at which they are joining it again. At that point there will
be a constant negative charge on the magnesium, and a constant number of magnesium ions
present in the solution around it.

Simplifying the diagram:

55
 this is a dynamic equilibrium. Ions are continually leaving and rejoining the surface.

Copper is less reactive and so forms its ions less readily. Any ions which do break
away are more likely to reclaim their electrons and stick back on to the metal again. You
will still reach an equilibrium position, but there will be less charge on the metal, and fewer
ions in solution.

If we write the two reactions as equilibria, then what we are doing is comparing the
two positions of equilibrium.

The position of the magnesium equilibrium . . .

. . . lies further to the left than that of the copper equilibrium.

56
 In the magnesium case, there is a lot of difference between the negativeness of the
metal and the positiveness of the solution around it. In the copper case, the difference is
much less.

This potential difference could be recorded as a voltage - the bigger the difference
between the positiveness and the negativeness, the bigger the voltage.

All we need to know is that the magnesium equilibrium lies further to the left than the
copper one. We need to know that magnesium sheds electrons and forms ions more readily
than copper does.

That means that we don't need to be able to measure the absolute voltage between the
metal and the solution. It is enough to compare the voltage with a standardised system
called a reference electrode.

The system used is called a standard hydrogen electrode.

Measuring standard electrode potentials (standard redox potentials)

The standard hydrogen electrode

The standard hydrogen electrode looks like this:

As the hydrogen gas flows over the porous platinum, an equilibrium is set up between
hydrogen molecules and hydrogen ions in solution. The reaction is catalysed by the
platinum.

This is the equilibrium that we are going to compare all the others with.

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 Standard conditions

The position of any equilibrium can be changed by changing conditions. That means
that the conditions must be standardised

The hydrogen pressure is 1 bar (100 kPa). 1 atmosphere) The temperature is 298 K
(25°C).

The concentration of the hydrogen ions in solution is also important. Changing

concentrations is one of the ways of changing the position of an equilibrium. Throughout
this topic, all ion concentrations are taken as being 1 mol dm-3.

Using the standard hydrogen electrode

The standard hydrogen electrode is attached to the electrode system you are
investigating - for example, a piece of magnesium in a solution containing magnesium ions.

Cells and half cells

The whole of this set-up is described as a cell. It is a simple system which generates a
voltage. Each of the two beakers and their contents are described as half cells.

The salt bridge

The salt bridge is included to complete the electrical circuit but without introducing
any more bits of metal into the system. It is just a glass tube filled with an electrolyte like
potassium nitrate solution. The ends are "stoppered" by bits of cotton wool. This stops too
much mixing of the contents of the salt bridge with the contents of the two beakers.

The electrolyte in the salt bridge is chosen so that it doesn't react with the contents of
either beaker.

58
 These two equilibria are set up on the two electrodes (the magnesium and the porous
platinum):

Magnesium has a much greater tendency to form its ions than hydrogen does. The
position of the magnesium equilibrium will be well to the left of that of the hydrogen
equilibrium.

The voltage measured would be 2.37 volts and the voltmeter would show the magnesium as
the negative electrode and the hydrogen electrode as being positive.

+0.4 is relatively more negative than +1.2.

Or -0.3 is relatively more positive than -0.9.

replacing the magnesium half cell by one with a piece of copper suspended in a
solution containing Cu2+ ions with a concentration of 1 mol dm-3. Choosing to use
copper(II) sulphate solution.

Copper forms its ions less readily than hydrogen does. Of the two equilibria . . .

There is less difference between the electrical charges on the two electrodes, so the
voltage measured will be less. This time it is only 0.34 volts.

The other major change is that this time the copper is the more positive (less negative)
electrode. The voltmeter will show the hydrogen electrode as the negative one and the
copper electrode as positive.

59
 The maximum voltage is called the electromotive force or emf.

The emf of a cell measured under standard conditions is given the symbol E°cell.

Saturated calomel electrode

The Saturated calomel electrode (SCE) is a reference electrode based on the
reaction between elemental mercury and mercury(I) chloride. The aqueous phase in
contact with the mercury and the mercury(I) chloride (Hg2Cl2, "calomel") is a
saturated solution of potassium chloride in water. The electrode is normally linked via
a porous frit to the solution in which the other electrode is immersed. This porous frit
is a salt bridge.

The electrode is written as:

Cell conventions

The cell in which a magnesium electrode is coupled to a hydrogen electrode is

represented like this:

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 You will often find variants on the way the hydrogen electrode is represented, such
as:

The convention is that you show the sign of the right-hand electrode (as you have
drawn it) when you quote the E°cell value. For example:

In the copper case:

Defining standard electrode potential (standard redox potential)

The values that we have just quoted for the two cells are actually the standard
electrode potentials of the Mg2+ / Mg and Cu2+ / Cu systems.

61
 The emf measured when a metal / metal ion electrode is coupled to a hydrogen
electrode under standard conditions is known as the standard electrode potential of that
metal / metal ion combination.

By convention, the hydrogen electrode is always written as the left-hand electrode of

the cell. That means that the sign of the voltage quoted always gives you the sign of the
metal electrode.

Standard electrode potential is given the symbol E°.

Here are a few typical standard electrode potentials:

metal / metal ion

E° (volts)
combination

Mg2+ / Mg -2.37

Zn2+ / Zn -0.76

Cu2+ / Cu +0.34

Ag+ / Ag +0.80

Remember that each of these is comparing the position of the metal / metal ion
equilibrium with the equilibrium involving hydrogen.

Here are the five equilibria (including the hydrogen one):

If you compare these with the E° values, you can see that the ones whose positions of
equilibrium lie furthest to the left have the most negative E° values. That is because they
form ions more readily - and leave more electrons behind on the metal, making it more
negative.

Those which don't shed electrons as readily have positions of equilibrium further to the
right. Their E° values get progressively more positive.

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Nernst Equation
The Nernst Equation is derived from the emf and the Gibbs energy under non-
standard conditions.

E o = E o reduction − E o oxidation
o
When E is positive, the reaction is spontaneous.

o
When E is negative, the reaction is not spontaneous.

Since the change in Gibbs free energy, ΔG, is also related to spontaneity of a
reaction, therefore, ΔG and E are related. Specifically,

ΔG = − nFE

where, n is number of electrons transferred in the reaction,

F is the Faraday constant (96500 C/mol)

E is potential difference.
Under standard conditions, this equation is then

ΔGo = − nFEo
Since,
ΔG = ΔG o + R T lnQ (1)

Substituting ΔG = − nFE and ΔG o = − n F E o into equation (1), we have:

− nFE = − nFEo + RTlnQ

Divide both sides of the equation above by −nF ,

E = E o − RT / nF lnQ (2)

Equation (2) can be rewritten in the form of log base 10:

E = E o − 2.303 RT / nF logQ (3)

At standard temperature T = 298K,

the 2.303RT / F = 0.0592 V,

so equation (3) turns into:

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 E = E o − 0.0592V / n log Q

The equation above indicates that the electrical potential of a cell depends upon the
reaction quotient Q of the reaction. As the redox reaction proceeds, reactants are
consumed, thus concentration of reactants decreases. Conversely, the products
concentration increases due to the increased in products formation. Cell potential
gradually decreases until the reaction is at equilibrium, at which ΔG = 0 .

Example:

For the Zn-Cu redox reaction:

Zn (s) +Cu 2+ (aq) →Zn 2+ (aq) +Cu (s) Eo cell = +1.10V
SOLUTION

Initially, [Cu2+] = [Zn2+] = 1.0 M at standard T = 298K As the reaction proceeds,

[Cu2+] decreases as [Zn2+] increases. Lets say after one minute, [Cu2+] = 0.05 M while
[Zn2+] = 5.0 M. According to Nernst, cell potential after 1 minute is:
E = E o − 0.0592V / n logQ

E = 1.10V − 0.0592V / 2 log 5.0 M / 0.05 M

E = 1.04V

As you can see, the initial cell potential is E =1.10V , after 1 minute, the potential drops to
1.04 V. As the reaction continues to progress, more Cu2+ will be consumed and more Zn2+
will be generated. As a result, the cell potential continues to decrease and when the cell
potential drops down to 0, the concentration of reactants and products stops changing. This is
when the reaction is at equilibrium.

At equilibrium, the reaction quotient Q = K eq . Also, at equilibrium,

ΔG =0 and ΔG = − nFE , so E =0 .

Therefore, substituting Q = K eq and E =0 into the Nernst equation, we have:

0 = E o −RT / nF ln K eq

At standard conditions, the equation above simplifies into:

0 = E o − 0.0592 / n log K eq

This equation can be rearranged into:

logK eq = nE o / 0.0592

The equation above indicates that the equilibrium constant Keq is proportional to the
standard potential of the reaction. Specifically, when:

64
  K > 1 , E o > 0 , reaction favors products formation.
 K < 1 , E o < 0 , reaction favors reactants formation.
This result fits Le Châtlier's Principle,which states that when a system at equilibrium
experiences a change, the system will minimize that change by shifting the equilibrium in the
opposite direction.

Problems
1. For this chemical reaction, Sn(s) + Pb 2+(aq) → Sn 2+(aq) + Pb (s) write out the
oxidation reaction and the reduction reaction. Create a cell diagram to match
your equations.
2. From the image above, of the cell diagram, write the overall equation for the
reaction.
3. If Cu2+ ions in solution around a Cu electrode is the cathode of a cell, and K+
ions in solution around a K electrode is the anode of a cell, which half cell has
a higher potential to be reduced?
4. What type of reaction provides the basis for a cell potential?
5. How is the cell potential measured and with what device is it measured?

Answers
1. oxidation: Sn(s) → Sn2+(aq) + 2e-(aq)
reduction: Pb2+(aq) + 2e-(aq) → Pb(s)
cell diagram: Sn(s) | Sn2+(aq) || Pb2+(aq) | Pb(s)
2. Cu(s) + 2Ag+(aq) → 2Ag(s) + Cu2+(aq)
3. Because the half cell containing the Cu electrode in Cu2+ solution is the
cathode, this is the half cell where reduction is taking place. Therefore, this
half cell has a higher potential to be reduced.
4. The redox reaction.
5. Cell potential is measured in volts (J/C). This can be measured with the use of
a voltmeter.

Examples
-
Calculate the potential of a cadmium electrode immersed in a 0.0100M Cd2+
solution if you know that Eo = - 0.4030 V
-
Calculate the potential of a platinum electrode immersed in a solution
prepared by saturating 0.0100M KBr with Br2. Eo = 1.065 V of Br2 electrod

65
There are two types of cell Galvanic and Electrolytic

Example

Calculate the theoretical potential for the cell Ag / AgCl (sat.) HCl ( 0.02 M) / H2
( 0.02 M), pt.

To calculate the equilibrium constant for redox reactions from standard electrode
potential:

n A ox + nm e- n A red ----------------------------1

m B ox + nm e- m B red ----------------------------2

Subtraction of the first equation from the second yield:

n A red + m B ox n A red + m B red

when system is in equilibrium

EA=EB

66