1Unit 1 Introduction

Definition of analytical chemistry

- Analytical chemistry is the science concerned with the systematic identification or
characterization of established chemical species and their determination to known
degrees of certainty at any level of concentration and in any matrix in which they may
occur or
- It is the science of obtaining, processing, and communicating information about the
composition and structure of matter or
- It is a scientific discipline that develops and applies methods, instruments and strategies
to obtain information on the composition and nature of matter in space and time

- It involves separating, identifying and determining the relative amounts of the

components in a sample of matter.

The discipline of analytical chemistry consists of qualitative, quantitative, characterization and

fundamental analysis.

Qualitative analysis: - An analysis in which we determine the identity of the constituent species
in a sample. Identification of elements or ions or compounds present in a sample. What chemical
species are present in a sample?
eg. - identifying the products of a chemical reaction,
- screening an athletes urine for the presence of a performance-enhancing drug
- Determining the spatial distribution of Pb on the surface of an airborne particulate.
Quantitative analysis:- An analysis in which we determine how much of a constituent species is
present in a sample. (Usually the given material is first analysed qualitatively and this is followed
by quantitative analysis). Determine the relative amounts of analytes in a sample, numerical
information, how much of each chemical species is present?
Eg determination of concentration of glucose level in blood
- Measuring the amount of gunpowder in hand, etc
Characterization analysis:- An analysis in which we develop new method for characterizing
chemical or physical properties of a sample . what are the materials chemical and physical
properties?

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Eg - Determinations of chemical structure, equilibrium constants, particle size, and surface
structure
A fundamental analysis: - An analysis whose purpose is to improve an analytical methods
capabilities. The purpose of a qualitative, quantitative, and characterization analysis is to solve a
problem associated with a sample. However, fundamental analysis is directed toward
improving the experimental methods used in the other areas of analytical chemistry. How does
this method work and how can it be improved?
Eg - Extending and improving the theory on which a method is based, studying a methods
limitations, and designing new and modifying old methods.
Analytical measurements are aimed at obtaining qualitative and quantitative information
about the composition and structure of various materials that have relevance to both
fundamental understanding as well as applications towards improving the quality of life.
The process of determining the level of any or all components in a material system is called
analysis. It can involve both physical and chemical processes. Any species that are the subjects
of either qualitative or quantitative analysis are known as analytes.
Analyte- is the components of a sample that are to be determined or the constituents of interest in
a sample.
Matrix- All other constituents in a sample except for the analytes.
1.2 Roles of analytical chemistry
Analytical chemistry an interdisciplinary science and often is called central science that
contributes to every branch of science. Analytical chemistry finds application in all the branches
of science like chemistry, physics, biology, geology, materials science, nuclear science and
technology, medicine, environment and industry. Obtaining precise and reliable data is the prime
requirement in the studies involving medical products, clinical evaluations, Environment impact
and remediation, and high tech products. These data may be used in decision making. Analytical
chemistry is vital in the following areas:
Quality control in the process industries of starting materials, intermediates and products. It is
required by most companies to control product quality (confirmation of purity or identification
of impurity).

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 Environmental analysis
- Monitoring and control of pollutants in streams that are to be released to the environment
(in gas, liquid or solid form)
- Measurement of pollutants in the environment (air/river/ground)
- NOx, SOx, hydrocarbons in atmosphere
- Organic chemicals (polychlorinated biphenyls, detergents)
- Toxic heavy metals (lead, cadmium, mercury)
Clinical and biological studies (blood, urine, feces, cellular fluids, etc., for use in diagnosis)
- Measurement of nutrients, including trace metals
- Measurement of naturally produced chemicals (cholesterol, sugar, urea)
- Measurement of drug levels in body
- Detection and/or analysis of biological components (i.e., proteins, DNA, RNA,
carbohydrates, metabolites, etc.).
Pharmaceutical analysis - establish the physical properties, toxicity, metabolites, quality
control, etc.
Forensic analysis - analysis related to criminology; DNA finger printing, finger print
detection; blood analysis.
Geological assays
- Measurement of metal concentrations in ores and minerals
- Measurement of oil/gas concentrations in rocks
Fundamental and applied research
- Chemical engineering: how much conversion (or separation) do we obtain under these
conditions?
- Organic molecule synthesis: what compound have we made?
1.3 Methods of chemical analysis
Analytical methods are classified as classical (wet chemical) and modern (instrumental)
methods.
Classical method
In the early years of chemistry, most analyses were carried out by separating the components of
interest (the analytes) in a sample by precipitation, extraction, or distillation. For qualitative
analyses, the separated components were then treated with reagents that yielded products that

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could be recognized by their colors, their boiling or melting points, their solubilities in a series of
solvents, their odors, their optical activities, or their refractive indexes. For quantitative
analyses, the amount of analyte was determined by gravimetrie or by volumetric measurements.

These classical methods for separating and determining analytes are still used in many
laboratories. The extent of their general application is, however, decreasing with the passage of
time and with the advent of instrumental methods to supplant them.
Instrumental method
Instrumental methods may be used to separate samples using chromatography, electrophoresis
or field flow fractionation. Then qualitative and quantitative analysis can be performed, often
with the same instrument and may use light interaction, heat interaction, electric
fields or magnetic fields. Often the same instrument can separate, identify and quantify an
analyte.
Table 1.1 chemical and physical properties those are useful for qualitative or quantitative
analysis for instrumental methods.
Analytical method can be classified according to size of sample. Such classification is arbitrary
and not sharp dividing line. The analysis may be classified as meso, semimicro, micro and
ultramicro. The last two categorize classified as trace analysis.
On the base of sample size, analytical methods are often classified as:
- Macro, the analysis of quantities of 0.1 g or more
- Meso(semimicro), dealing with quantities ranging from 10-2g to 10-1 g
- Micro, for quantities in the range 10-3 g to 10-2 g
- Submicro, for samples in the range 10-4 g t0 10-3 g
- Ultra micro, for quantities below 10-4 g.
The constituent in the sample may be classified as major is the one present 1-100% of the sample
under investigation, minor is one present in the range of 0.01 to 1%, trace (<0.01%). A few parts
per million or less constituent can be classified as ultratrace.
Analysis can be classified as complete or partial.

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1.4 Steps in quantitative chemical analysis
Atypical quantitative analysis involves a sequence of steps. In some instances, one or more of
these steps omitted. For example if the sample is already a liquid, we can avoid the dissolution
steps.
1. Identify the problem-
Determine type of information needed (qualitative, quantitative, characterization, or
fundamental), Identify context of the problem. The type of information needed and the problems
context are essential to designing an appropriate experimental procedure.
2. Choosing the method
One of the first questions to be considered in the selection process is the level of accuracy
required. A second consideration related to economic factors is the number of samples to be
analyzed. The complexity of the sample and the number of components in the sample always
influence the choice of method to some degree.
3. Acquiring the sample
Sampling - is the process of collecting a small mass of a material whose composition accurately
represents the bulk of the materials being sampled. Sampling is frequently the most difficult step
in an analysis and the source of greatest error. The final results of an analysis will never be any
more reliable than the reliability of the sampling step.
4. Processing a sample
Under certain circumstances, no sample processing is required prior to the measurement step.
Under most circumstances, we must process the sample in any of a variety of different ways.
The first step in processing the sample is often the preparation of a laboratory sample.
Preparing a Laboratory Sample - A solid sample is ground, mixed to ensure homogeneity, and
stored for various lengths of time before analysis. Because any loss or gain of water changes the
chemical composition of solids, it is a good idea to dry samples just before starting an analysis.
Alternatively, the moisture content of the sample can be determined at the time of the analysis in
a separate analytical procedure. Liquid samples are subject to solvent evaporation. If the analyte
is a gas dissolved in a liquid, analyte must be kept inside a second sealed container to prevent
contamination by atmospheric gases. Extraordinary measures, including sample manipulation
and measurement in an inert atmosphere, may be required to preserve the integrity of the sample.

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Replicate sample
Replicates are portions of a material of approximately the same size that are carried through an
analytical procedure at the same time and in the same way. Replication improves the quality of
the results and provides a measure of their reliability. Quantitative measurements on replicates
are usually averaged, and various statistical tests are performed on the results to establish their
reliability.
Preparing Solutions: Physical and Chemical Changes
Ideally, the solvent should dissolve the entire sample, including the analyte, rapidly and
completely. The sample may require heating with aqueous solutions of strong acids, strong
bases, oxidizing agents, reducing agents, or some combination of such reagents. It may be
necessary to ignite the sample in air or oxygen or perform a high-temperature fusion of the
sample in the presence of various fluxes.
5. Eliminating the interferences
Species other than the analyte that affect the final measurement are called interferences, or
interferents. Interference is a species that causes an error in an analysis by enhancing or
attenuating (making smaller) the quantity being measured. Techniques or reactions that work for
only one analyte are said to be specific. Techniques or reactions that apply for only a few
analytes are selective.
The matrix, or sample matrix, is all of the components in the sample containing an analyte.
6. Calibrating and measuring concentration
Ideally, the measurement of the property (X) is directly proportional to the concentration.
CA = kX, where k is proportionality constant
7. Calculating results
Computing analyte concentrations are based on the raw experimental data collected in the
measurement step, the characteristics of the measurement instruments, and the stoichiometry of
the analytical reaction.
8. Evaluating results by estimating their reliability
Analytical results are incomplete without an estimate of their reliability.

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 Unit two Ionic equilibria

2.1 Acid-base equilibria

Definition of acids and bases

Arrhenius definition
-Acids are a hydrogen containing substance that dissolved in water release H+ ions.
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eg. HCl H+ + Cl-
-Bases are a hydroxide containing substance that dissolved in water release OH- ions.
2
NaOH Na+ + OH-
When acids and bases react according to this theory, the hydrogen and hydroxide ions neutralize
each other forming water
H+ + OH H2O
Limitation of Arrhenius definition
- It is limited to only aqueous solutions and requires dissociation of the substance.
- It does not explain the acidic behaviour of some substances which do not contain
hydrogen. For example, AlCl3. Similarly it does not explain the basic character of
substances like NH3 and Na2CO3 which do not have a hydroxide groups.
Bronsted & Lowry definition - an acid-base reaction involves a transfer of protons from one
substance to another. Acids are proton donors while bases are proton acceptors.
HCl + H2O H3O+ + Cl- ; HCl donates H+ to water, hence acid.
NH3 + H2O NH4+ + OH; NH3 takes H+ from water, hence base.
For the backward reaction, NH4+ donates H+, hence it is an acid; OH accepts H+, hence it is a
base, NH4+ & NH3 form a conjugate acid base pair.
Conjugate acid-base pairs consist of two species in acid- base reaction, one acid and one
base that differ by gain or loss of a proton. The acid is a conjugate acid of the base where as
the base is the conjugate base of the acid. i.e NH4+ is the conjugate acid of NH3, and NH3 is the
conjugate base of NH4+. The members of each conjugate pair are designated by the same
numerical subscripts.

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The weaker the acid, the stronger its conjugate base (and vice versa) and the weaker the base,
the stronger its conjugate acid and vice versa. Eg HCl &HF
Lewis definition of acids and bases
As discussed above the Brnsted- Lowry concept does not depend on the nature of the solvent ( a
short coming of the Arrhenius concept removed ). However, like Arrhenius concept it does not
explain the acidity of the substances which do not have a hydrogen atom (e.g., AlCl3) and the
basicity of the substances devoid of a OH- group (e.g., Na2CO3).
- Base is a substance that donates an electron pair (nucleophile) while an acid is one that
accepts an electron pair (electrophile) to form a coordinate bond.
Eg. NH3 +BF3 H3N--BF3
Lewis acids are
i. Molecules in which central atom has incomplete octet. (e.g. BF3, AlCl3 etc.)
ii. Molecules which have a central atom with empty d orbitals (e.g. SiX4, GeX4, PX3, TiCl4 etc)
iii. Simple Cations: Though all cations can be expected to be Lewis acids, Na+, Ca++, K+ etc.
show no tendency to accept electrons. However H+, Ag+ etc. act as Lewis acids.
iv. Molecules having multiple bond between atoms of dissimilar electronegativity. e.g. CO2,
SO2, SO3
Lewis bases are
i. Neutral species having at least one lone pair of electrons. E.g. NH2NH2, ROH, etc
ii. Negatively charged species (anions). e.g. CN-, OH-, Cl-, etc.

Amphoteric species- are species that possess as both an acidic and a basic properties. Eg HCO3-,
H2O, HSO3--, HS-
HCO3- (aq) + HF (aq) H2CO3 (aq) + F- (aq)
HCO3- (aq) + OH- (aq) CO32- (aq) + H2O (l)
Autoprotolysis (autoionization)- involves the spontaneous reaction of molecules of a substance
to give a pair of ions. Amphoteric solvents undergo self ionization.

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Strength of acid and bases
Strong acids or bases are completely dissociated in aqueous solution. The equilibrium lies to the
right. The value of Keq is very large. for acid HClO4, H2SO4, HI, HBr, HCl, HNO3, e.g. HCl(aq)
+ H2O(l) H3O+ (aq) + Cl- (aq), for strong base G-1 metals G-2 metals except Be.
Weak base and weak acid
Weak acid or weak base do not react with water completely or dissociated completely.
For example a weak acid HA,
HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Apply the law of mass action of chemical equilibrium, the equilibrium constant K is

The concentration of [H2O] is constant,

, Here Ka is dissociation constant of the weak acid. Ka value

ids depend on temperature. The higher the Ka value is the stronger the acid.
Weak base is not completely protonated by water.

, the equilibrium constant for the reaction is

, Kb is the base dissociation constant.

The dissociation of water
Water can act as a very weak acid and base. A small concentration of H3O+ and OH- are formed
in water due to its self-ionization.

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Since the concentration of water molecule is constant, [H3O+][OH-] = K[H2O]2 = Kw (a new
constant) Kw is called the ionic product constant of water. The electrical conductivity of purified
water at 25 oC show that [H3O+] = [OH-] = 1.00 x10-7 molL-1.
Kw = [H3O+][OH-] = (1.00 x10-7) (1.00x10-7) =1.00 x10-14 mol2 L-2 at 25 oC.
If the [H3O+] > [OH-] the solution is acidic
[OH-] > [H3O+] the solution is basic
[H3O+] = [OH-] the solution is neutral

pH and pOH Calculations

The pH and pOH scales are used to represent the acidity or basicity of an aqueous solution.

Solving the pH and pOH expressions for hydronium ion and hydroxide ion concentration,
respectively, allows calculation of [H3O+] and [OH] from pH and pOH.

We can derive an expression relating pH and pOH for aqueous solutions at 25oC.

From this equation in acidic solutions (low pH, high [H3O+]) have a high pOH (low [OH]) and
basic solutions (high pH, low [H3O+]) have a low pOH (high [OH]).
The Relationship between Ka and Kb
The strongest acids have large Ka values and small pKa values [pKa = log (Ka)]. As acid
strength increases, pKa decreases.
The strongest bases have large Kb values and small pKb values [pKb = log (Kb)]. As base
strength increases, pKb decreases.
The conjugate base of a strong acid has a very small Kb value. In general, as acid strength
(and Ka) increases, the strength of the acids conjugate base decreases.

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 The conjugate acid of a strong base has a very small Ka value. In general, as base strength
(and Kb) increases, the strength of the bases conjugate acid decreases.
This relationship can be illustrated mathematically using the Ka and Kg expressions for a
conjugate acidbase pair.

Notice that as Ka increases, acid strength increases and Kb for the conjugate base must decrease.
Common ion effect
The common-ion effect is used to describe the effect on an equilibrium involving a compound
that adds an ion that is common to an existing equilibrium. LE CHATELIER'S PRINCIPLE
states that when a stress is applied to a system at equilibrium, the system readjusts to relieve or
offset the stress and the system reaches a new state of equilibrium. Adding a common ion
prevents the weak acid or weak base from ionizing as much as it would without the added
common ion. If a common ion is added to a weak acid or weak base equilibrium, then the
equilibrium will shift towards the left or reactants. The source of the common ion is typically
provided by adding a strong acid, a strong base or a soluble salt to the equilibrium reaction
mixture.
Buffer solutions
A buffer solution is the one that resists change in pH on adding small amount of strong acid or
base. It contains conjugate acid- base pairs. The change in pH in buffers is inhibited by the
common ion effect.

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In laboratory reactions, in industrial processes and in the bodies of plants and animals, it is often
necessary to keep the pH nearly constant despite the addition of acids and bases. The oxygen
carrying capacity of haemglobin in our blood and activity of the enzymes in our cells depends
very strongly on the pH of our body fluids. pH of the blood is very close to 7.4 and pH of saliva
is close to 6.8. Fortunately, animals and plants are protected against sharp changes in pH by the
presence of buffers.
There are two kinds of commonly used buffer-solutions
i. Acidic buffers whose pH less than 7. It consists of a weak acid and a soluble ionic salt of
the weak acid e.g. CH3COOH & CH3COONa
ii. Basic buffers whose pH above 7. It consists of a weak base and a soluble ionic salt of the
weak base e.g. NH3 & NH4Cl
Henderson-Hasselbalch Equation
This equation relates the pH of a given buffer solution to the concentrations of its components
viz. weak acid / salt or weak base / salt. The derivation of acidic buffer system is as follows:
In acetic acid - sodium acetate buffer the central equilibrium is

, which is characterized by acidic dissociation constant

Rearrange,

The concentration of undissociated acetic acid can be taken as total acid concentration [Acid]
and that of sodium acetate as the total salt concentration [Salt]. In the light of this the above
equation may be rewritten as

Taking logarithm and multiplying throughout by (-1) we get

,
This equation is known as Henderson-Hasselbalch equation. A similar expression can be
derived for a basic buffer

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Exercise
1. Calculate the pH of sodium acetate buffer solution that is 0.1 M in acetic acid and 0.1 M in
sodium acetate. (Ka of acetic acid is 1.8x10-5 mol L-1) Ans pH = 4.73
2. Calculate the pH of ammonium hydroxide ammonium chloride buffer solution that is 0.1 M
in ammonium hydroxide and 0.01 M in ammonium chloride. ( pKb of NH4OH = 9.25). ans
pH = 5.75
BUFFER CAPACITY
Buffering capacity is the amount of acid or base that can be added to a buffer without causing a
large change in pH. The buffer capacity is a measure of the effectiveness of a buffer.
1
Buffer capacity=

The effectiveness of a buffer depends on two factors

i. The relative amounts of acid and base
ii. The absolute concentrations of acid and base.
- Buffer capacity is greater when larger amounts of HA and A- are present.
- pH will stay relatively constant as long as [HA] and [A-] are greater than the amount of
acid or base added.
- Buffers work best when [HA] and [A-] are approximately equal, pH = pKa. For buffers to
be effective, the ratio of Base:Acid should be between 1:10 to 10:1.
- The buffering range is the pH range the buffer can be effective. The effective pH range
of a buffer is pKa 1, when choosing an acid to make a buffer, choose one whose pKa is
closest to the pH of the buffer.
Exercise
1. The pH of a buffer solution containing 0.5 mol/L of CH3COOH and 0.5 mol/L CH3COONa
has been found to be 4.76. What will be the change of pH of this solution after
a) 0.1 mol HCl has been added to the buffer?
b) 0.02 mole NaOH has been added to the buffer
(Assume that the volume is unchanged. Ka = 1.75 10-5)

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Salt Hydrolysis
What is hydrolysis? Hydro- means water, and lysis, means breaking.
It is the reaction of anything with water.
The aqueous solutions of certain salts also behave as acids or bases. They do so because of the
hydrolysis of the cation or anion or both. Depending on the behaviour towards hydrolysis there
are four different types of salts.
1. Salt of strong acid and strong base
2. Salts of Weak acids and Strong bases
3. Salts of Weak bases and Strong acids
4. Salts of Weak acids and Weak bases
BRONSTEDLOWRY CONCEPT OF HYDROLYSIS
HA and A are conjugate acid-base pair

Since HA is a weak acid (poor proton donor), its conjugate base, A-, must be relatively strong
(good proton acceptor). Owing to this fact, A ions tend to react with water by accepting proton
from the water to form HA molecule (anionic hydrolysis),

, The presence of OH ions makes the solution basic.

Similarly, BOH and B+ are a conjugate acid-base pair. Since BOH is a weak base, its conjugate
acid, B+, would be relatively strong. Thus B+ would accept OH ions from water to form BOH
molecules.

, The presence of excess H+ ions makes the solution acidic

Salt of strong acid and strong base
The cations of the strong bases and the anions of the strong acids do not get hydrolyzed.
Therefore the salts of this category do not show any acid-base behavior and are neutral. e.g.
NaCl, KNO3, RbClO4, etc.
NaCl(s) H 2O(l ) Na (aq) Cl (aq)
Since HCl is a strong acid, Cl is very weak base. Cl is unable to accept a proton (H+) from an
acid, particularly water. That is why Cl does not hydrolyse. It cannot generate OH ions as
follows:

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The pH of sodium chloride solution remains unaffected.
Salts of Weak acids and Strong bases
Hydrolysis is a reversible reaction. The equilibrium constant derived by application of Law of
Mass action to a hydrolysis (or hydrolytic) reaction is called the Hydrolysis constant or
Hydrolytic constant. The hydrolysis constant is represented by Kh.
Example: CH3COONa, NaCN, etc.
The general hydrolysis reaction of a salt of weak acid (HA) and strong acid can be written as

The equilibrium constant expression is

-------------------------------- (1)
Relation between Kh, Kw and Ka
The ionic product of water, Kw, is expressed as

------------------------ (2)
From the acid dissociation constant, Ka, is expressed

------------------------------ (3)
Divided equation (2) by (3)
Kw
Kh -------------------------------------- (4)
Ka
The degree of hydrolysis () is the fraction of the salt which has undergone hydrolysis when
equilibrium is established.
Suppose we start with one mole of the salt dissolved in V litres of solution. Then the equilibrium
concentrations are:

Hence the hydrolysis constant Kh is given by

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If is small, (1 ) may be taken as equal to one. Then,

Where C- the initial concentration of the salt

Derivation of pH
pH of an aqueous solution of weak acid and strong base can be derived as follows :

and , but

,
It is evident that pH of the solution will always be greater than 7. Thus aqueous solution of salt
of weak acid and strong base will be always alkaline.
Salts of Weak bases and Strong acids
The hydrolysis of a salt of a weak base BOH (e.g, NH4OH) and a strong acid may be represented
by the equation:

The hydrolysis constant, Kh, of the reaction is

----------------------- (1)
Relation between Kh, Kw and Kb
The ionic product of water Kw is expressed as :

----------------------- (2)
From the dissociation constant of weak base, Kb,

----------------- (3)
Divided equation (2) by (3)

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 Kw
Kh ---------------------------------------- (4)
Kb
Relation between Hydrolysis constant and degree of hydrolysis
Suppose we start with one mole of the salt dissolved in V litres of solution. Then the
concentrations when equilibrium is attained are :

Applying the Law of Mass Action, the hydrolysis constant, Kh is given by the expression

When is small, (1 ) may be considered as equal to one. Then we have

Where C- is the initial concentration of the salt

Derivation of pH
From the above reaction:

and substitute the value of

, taking logarithm and reverse the sign

1 1
pH 7 pKb log C
2 2
In this case it is evident that pH will always be less than 7. Thus, the solution of a salt of weak
base and strong acid will always be acidic.

SALTS OF WEAK ACIDS AND WEAK BASES

In this type of salt, both the anion of weak acid (X) and the cation of weak base (B+) undergo
hydrolysis simultaneously.

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The hydrolysis constant expression can be

------------------------------------------ (1)
Relation between Kh, Kw, Ka and Kb
Applying Law of Mass Action to the ionisation of weak acid, HX, weak base, BOH, and water,
we can write

Dividing (4) by (3) and (2), we have

Kw
Kh
KaxKb
Relation between Hydrolysis constant and Degree of Hydrolysis
Let us start with 1 mole of the salt of a weak acid and weak base. If is the degree of hydrolysis
(fraction hydrolysed), the equilibrium concentrations are :

Substituting these in the hydrolysis constant expression

Derivation of pH

If pKa = pKb, pH = 7, the solution is neutral

If pKa > pKb, the acid is weaker than base, pH > 7, the solution is alkaline

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 If pKa < pKb, the acid is stronger than base, pH < 7, the solution is acidic
Exercise: Calculate the hydrolysis constant and pH of 0.625 M solution of CH3COONa. Ka
1.754 10 5, ans pH = 9.28

SOLUBILITY EQUILIBRIA
Solubility is the quantity of solute that dissolves in a given quantity of solvent at a particular
temperature. Unit of solubilitys are mol/L, g/L, etc
For molar solubility, the units are mol/L, Molar Solubility = concentration of the dissolved salt;
ion concentrations are related to the solubility of the salt by their coefficients.
For MgS, , the solubility of MgS = [MgS]
Solubility rule
- Most nitrate (NO3) salts are soluble.
- Most salts containing the alkali metal ions (Li+, Na+, K+, Rb+, Cs+) and the ammonium ion
(NH4+) are soluble.
- Most chloride (Cl), bromide (Br) and iodide (I) salts are soluble. Notable exceptions are salts
containing the ions Ag+, Pb2+ and Hg22+.
- Most sulfate (SO42) salts are soluble. Notable exceptions are BaSO4, PbSO4, HgSO4 and
CaSO4.
- Most hydroxide salts are only slightly soluble. The important soluble hydroxides are NaOH and
KOH. The compounds Ba(OH)2, Sr(OH)2 and Ca(OH)2 are marginally soluble.
- Most sulfide (S2), carbonate (CO32), chromate (CrO42) and phosphate (PO4 3) salts are only
slightly soluble.
Some ionic compounds (salts) dissolve readily in water and dissociate into their ions. However,
other salts are only slightly or sparingly soluble in water and form solid precipitates in aqueous
solutions. These insoluble salts dissolve to a small extent and form a saturated solution. The
undissolved solid and the dissociated ions in solution establish a heterogeneous an equilibrium
system.

NB When a slightly soluble ionic compound is mixed with water, one of the following two
phenomena may occur:
1. The amount of ionic compound is very small (Ksp 1). As such:

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 - it completely dissolves (completely dissociates into ions)
- an unsaturated solution is formed
- no undissolved solid remains
2. The amount of ionic compound is relatively large (Ksp << 1). As such:
- it partially dissolves in water (partially dissociates into ions)
- a saturated solution is formed
- some of the solid remains undissolved
- an equilibrium occurs between the undissolved solid and the ions in the solution
Solubility equilibrium is a dynamic equilibrium between a solute and a solvent in a saturated
solution in a closed system because the rate of dissolving equals the rate of precipitation and both
reactions continue to occur even though there are no macroscopic changes.
Solubility product
Solubility product is defined as the product of ionic concentration when dissolved ions and un-
dissolved ions are in equilibrium.
The solubility product constant (Ksp) is the equilibrium constant for the solubility equilibrium
of a slightly soluble (or nearly insoluble) ionic compound. It is equals the product of the
equilibrium concentrations of the ions, raised to a power equal to the number of the ions in the
formula of the compound. Ksp is constant at a given temperature.
For a sparingly soluble salt in the form MaXb dissolved in water the Ksp expression can be
written as
M a X b ( s) aM c (aq) bX d (aq)

Ksp [M c ]a [ X d ]b , where Ksp is the solubility product constant

Example: 1. Write the solubility equilbrium reaction and the Ksp expression for
a) MgF2 b) AgCl c) Ca3(PO3)2
3. The solubility of Lead (II) arsenate, Pb3(AsO4)2, is 3.0 x 10-5 g/L. Calculate its Ksp
The Reaction Quotient
Whenever two solutions containing ions are mixed, there is the possibility that a precipitate may
form. If the concentrations of the ions is 0.1 M or higher any compound having low
solubility will precipitate; however, if the concentrations of the ions is less than 0.1 M then a
calculation must be performed to determine if a precipitate will form. The reaction quotient

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 (Q), or trial ion product (T.I.P.) has the same form as the Ksp, except that the concentrations
of the reactants and products are nonequilibrium concentrations. From calculating the reaction
quotient, we can determine if dissolution or precipitation will occur.
- If Q = Ksp, the solution is saturated. The dissolution and precipitation occur at equal rates
- If Q < Ksp, the solution is unsaturated. Precipitation does not occur.
- If Q > Ksp, the solution is supersaturated. The solution will likely have rapid
precipitation of solid.
Exercise: If the Ksp for PbCl2 is 1.8 104, will a precipitate form when 200.0 mL of 0.015 M
NaCl is mixed with 100.0 mL of 0.060 M Pb(NO3)2?

Factor affecting solubility

The solubility of insoluble salt can be affected by
- Temperature
- Presence of common ion
- pH
- complex ion
- presence of other salts
- TEMPERATURE:
Endothermic dissolutions lead to greater solubility at elevated temperature; exothermic
dissolutions lead to less solubility at elevated temperature.
THE COMMON ION EFFECT AND SOLUBILITY
- The effect of the common ion is to decrease the solubility of the salt

pH AND SOLUBILITY
Addition of an acid can increase the solubility of an insoluble salt if the salt contains a basic
anion.

Adding a strong acid (e.g. HCl) provides H+ ions:

Addition of H+ causes [F-] to decrease (i.e. F- is removed); so the equilibrium shifts right to form
more F-, thus the solubility of the salt increases as the salt dissolves.

21
All salts that contain strong conjugated base will have their solubility increased in an acidic
solution. In acidic solutions the basic anion reacts with the acid, forcing more of the salt to
dissolve to reach equilibrium.
Salting effect
Solubility of electrolytes is also influenced by salts having no common ion. The solubility of
slightly soluble salt can be increase due to the presence of either of common or uncommon ions.
Salting effect increases with the number of electrical charges upon the ions involved in the
effect.
Example: Effect of sodium sulphate on the solubility of magnesium sulphate is greater than
effect of potassium chloride on the solubility of silver chloride. This is because increase in
number of charges will decrease the effective concentration of ions due to interionic interaction
between charges species.
Effect of complex formation on solubilty
Complex ions are ions that form from transition metal ions attached to molecules or anions by
coordinate covalent bonds. Formation of complex ions can increase the solubility of an insoluble
salt.

COMPLEXATION EQUILIBRIA

A complex is a combination of separate groups of atoms, molecules or ions that join together to
form a single large molecule or ion. A single ion or atom serves as the central point of the
complex. This central atom has vacant electronic orbitals that provide a means for bonding to
occur with unshared electrons on the other atoms, ions or molecules. The final charge of the
complex is the sum of all the charges of the individual components. Thus a complex in solution
can have a positive, negative or zero charge.

The product of the reaction of a Lewis acid with a Lewis base is an acidbase complex or
complex ion. The new bond formed between the Lewis acid and Lewis base is called a
coordinate-covalent bond because both bonding electrons come from a single species.

22
- The metal cation is a Lewis acid which is atom or molecule with at least one empty
valence-shell
- The ligands are Lewis bases which is an atom or molecule that contains at least one pair of
nonbonding electrons. A ligand may be conveniently classified on the basis of the number of
points attachement to metal ion
Monodentate is a ligand bound to a metal ion only one point of attachment, eg Cl-, NH3,
Bidentate- the molecule has two donor groups eg, ethylene diamine
Multidentate- more than two donor groups per molecule, eg EDTA
- For a metal cation, Mn+, and a neutral ligand, L, the complex formation is given by the
equilibrium:
n n
M mL M ( L) m
n Where Kf = formation or stability constant.
[ M ( L) m ]
Kf
[ M n ][ L] m

Formation constants are divided into two categories.

I. Stepwise formation constants, which are designated as Ki for the ith step, is the formation
constant for a metalligand complex in which only one ligand is added to the metal ion or to a
metal ligand complex
II. cumulative formation constants, (i) is the formation constant for a metalligand complex
in which two or more ligands are simultaneously added to a metal ion or to a metalligand
complex

Equilibrium constants for complexation reactions involving solids are defined by combining
appropriate Ksp and Kf expressions. For example the equilibrium constant for the following
complexation reaction

a) 3 = Ksp xK1x K2

23
Complex dissociation equilibrium constant (Kd) is the equilibrium constant for a reaction in
which a metalligand complex dissociates to form uncomplexed metal ion and ligand. The
dissociation constant is equal to the inverse of Kf (Kd = 1/Kf)

REDOX EQUILIBRIUM

The term redox is used as an abbreviation for the processes of reduction and oxidation. These
two processes usually occur simultaneously. Redox reactions, electrons are not shared, but are
transferred from one reactant to another. The separate equations showing which substance gains
electrons and which substance loses electrons are known as half-equations.
- Oxidation is defined as the loss of electrons
- Reduction is defined as the gain of electrons.
Oxidising agents (oxidant) are substances which accept electrons; reducing agents (reductant)
are substances which donate electrons.
Example
When a piece of iron is immersed in copper (II) sulphate solution, it soon becomes coated with
copper. The reaction may be represented by the ionic equation:

,
The reducing agent is Fe and it is oxidized to Fe2+ (aq) :
Oxidation half-equation: Fe(s) Fe2+ (aq) + 2 e-
The oxidising agent is Cu2+ (aq) and it is reduced to copper:
Reduction half-equation: Cu2+ (aq) + 2 e- Cu(s)
The reducing or oxidizing of a substance depends on its reduction potential.
Electrochemical cell
A device for producing an electrical current from a chemical reaction (redox reaction) is called
an electrochemical cell.
There are two types of electrochemical cells.

24
 i. Galvanic(voltaic) cell- a chemical reaction spontaneously occurs to produce electrical
energy (electricity). For example lead storage battery and flashlight battery
ii. Electrolytic cell- electrical energy used to nonspontaneous chemical reaction to occur.
Eg electrolysis of water.
In both these cell the electrode at which oxidation occurs is anode (-) and reduction occurs in a
cathode (+).
Cell diagram or Representation of a Cell
In 1953 IUPAC recommended the following conventions for writing cell diagrams.
(1) a single vertical line (|) represents a phase boundary between metal electrode and ion
solution (electrolyte).
(2) A double vertical line (||) represents the salt bridge, porous partition or any other means
of permitting ion flow while preventing the electrolyte from mixing.
(3) Anode half-cell is written on the left and cathode half-cell on the right.
Example

Electrode Potential
It is impossible to obtain the electrode potential for a single half-cell. E.m.f. values can only be
measured for a complete circuit with two electrodes. Since electrode potential depend on
temperature, concentration and also pressure, it is necessary to standardize them if they are to be
compared.
The standard conditions chosen are similar to those for thermochemical measurements:
1. All solutions have a concentration of 1 moldm-3.
2. Any gas involved has a pressure of 1 atmosphere.
3. The temperature is 298 K (25 oC).
4. Platinum is used as the electrode when the half-cell system does not include a metal.
The standard electrode potential of an electrode ( half-cell ) is thus defined as the e.m.f. of a
cell in which the electrode on the left is a standard hydrogen electrode and that on the right is the
standard electrode in question.

25
Standard electrode potentials are sometimes called standard reduction potentials because they
related to the reduction of the more oxidized species.

A standard reduction potential is a measured of the tendency for reduction to occur. It is also a
measure of the strength of the oxidising agent to accept electrons.
The stronger an oxidising agent, the more positive its electrode potential.

A strong reducing agent has a large negative electrode potential.

To calculate e.m.f. of a cell

1. The half-cell with the more positive electrode potential is the half-cell which reduction occurs,
2. The half-cell with the less positive electrode potential is the half-cell which oxidation occurs,
3. The e.m.f. of an electrochemical cell is given by :

Example calculate the e.m.f. of the cell based on the following data

26
Solution
Eocell = Eoright Eoleft
= -0.25V- (-0.76V)
= +0.51V
Prediction of the feasibility of redox reactions
The standard electrode potentials enable us to predict whether a redox reaction is spontaneously
or not. In general, redox reactions with an overall positive standard cell potential ( cell e.m.f. )
are energetically feasible whereas those with an overall negative value are not so.
If E0cell > 0 the reaction will proceed from left to right as written.
If E0 cell = 0 the reaction is at chemical equilibrium.
If E0 cell < 0 the reaction will not proceed in the direction written, but it will take place in the
opposite direction.
Example Predict whether the reaction is feasible or not.

Redox reactions having a positive cell e.m.f. are feasible reactions and will take place
spontaneously. However, since electrode potentials are affected by changes in concentration and
temperature, a prediction based on standard electrode potential values may not be valid under
conditions which are not standard.
THE NERNST EQUATION
The general Nernst equation correlates the Gibb's Free Energy G and the EMF of a chemical
system known as the galvanic cell. For the reaction

27
aA+bB cC+dD

[C ]c [ D]d
and Q
[ A]a [ B]b
G = G + RTln(Q), but G = -nFEcell
-nFEcell = -nFEcell + RTln(Q)
Ecell = Ecell - (RT/nF)ln(Q)
2.303RT
Ecell = Eocell- log( Q)
nF
Where Eocell- standard electrode potential
R- Gas constant (8.314 J mol-1 K-1)
T- Temperature (K)
n-number of electrons transferred in half reaction
F-Faraday constant (96485 C)
Q- Reaction quotient
At 298 K the Nernst equation can be written as
Ecell = Ecell - (0.0591/n)log(Q), where Q has the same form as the equilibrium constant.
Example
Calculate the equilibrium constant for the reaction between silver nitrate and metallic zinc.

28
CHAPTER THREE
STATISTICAL EVALUATION OF ANALYTICAL DATA
3.1 Mean, Standard deviation, Variance
A. Measures of Central Tendency
Two common ways to report this estimate of central tendency are the mean and the median.
Mean ( X ) is the numerical average value of a set of data which obtained by dividing the sum of
the individual measurements by the number of measurements. It is the most common estimator
of central tendency.
n

Xi
X i 1
, where Xi- is the ith measurement
n
n- is the number of independent measurements.
Median (Xmed) is the middle value when data are ordered from the smallest to the largest value.
When the data include an odd number of measurements, the median is the middle value. For an
even number of measurements, the median is the average of the n/2 and the (n/2) + 1
measurement, where n is the number of measurements. The median, however, provides a more
robust estimate of central tendency since it is less sensitive to measurements with extreme values
B. Measures of Spread
Three common measures of spread are range, standard deviation, and variance.
Range (w) is the difference between the largest and smallest values in the data set.
w = Xlargest Xsmallest
The range provides information about the total variability in the data set, but does not provide
any information about the distribution of individual measurements.
Standard Deviation(s) is a statistical measure of the average deviation of data from the datas
mean value. The smaller the standard deviation, the more closely the data are clustered about
the mean.
The absolute standard deviation, s, describes the spread of individual measurements about the
n

( Xi X )
i 1
2

mean and is given as s Where Xi is one of n individual measurements

n 1
and X is the mean. The quantity n-1 is called the degrees of freedom.

29
For an infinite set of data, the mean is designated by the lowercase Greek letter mu, (the
population mean), and the standard deviation is written as a lowercase Greek sigma, (the
population standard deviation). We can never measure and , but the values of X and s
approach and as the number of measurements increases.
The relative standard devation (sr) is reported as
s
sr
X
The percent relative standard deviation or coefficient of variation is
s
%s r x100
X
Variance (s2) is the square of the standard deviation
3.2 Accuracy and precision of measurements

In any measurements, accuracy and precision are important. Although the words are used
interchangeably in casual conversation, they have different meanings. Measurement errors are
unavoidable, so "error" in this context does not mean "mistake." We may have measured the true
value, but we are never certain that we have done so.
Accuracy is a measure of the agreement of a particular measurement with the true (or
accepted) or theoretical value of the parameter under the conditions. Accuracy has a sign that
indicates whether the experimentally measured value is high (+) or low (-) compared to the true
value.
Accuracy is usually expressed as either an absolute error (E) or percent relative error (Er).
X
E = X , Er = x100

Precision is a measure of the spread of data about a central value whose describes the agreement
among several determinations of the same quantity. The better the precision, the lower the
difference among the values. Another way of saying this is that the results are highly
reproducible. High precision is achieved with quality instruments and careful work. Precision
may be expressed as the range, the standard deviation, or the variance. Precision is commonly
divided into two categories: repeatability and reproducibility.
Repeatability is the precision obtained when all measurements are made by the same analyst
during a single period of laboratory work, using the same solutions and equipment.

30
Reproducibility is the precision obtained under any other set of conditions, including that
between analysts, or between laboratory sessions for a single analyst. Since reproducibility
includes additional sources of variability, the reproducibility of an analysis can be no better than
its repeatability.

3.3 Errors in analytical results

Every measurement has some uncertainty, which is called experimental error. Error is a measure
of bias in a result or measurement. Experimental error is classified as either systematic or
random.
Systematic Error
Systematic error, also called determinate error which is a consistent error that can be detected
and corrected. With care and cleverness, you can detect and correct a systematic error. For
example, a pH meter that has been standardized incorrectly produces a systematic error.
It affects the accuracy of an analysis. All the individual measurements are either too large or too
small. A positive determinate error results in a central value that is larger than the true value,
and a negative determinate error leads to a central value that is smaller than the true value. Both
positive and negative determinate errors may affect the result of an analysis, with their
cumulative effect leading to a net positive or negative determinate error. Determinate errors may
be divided into four categories: sampling errors, method errors, measurement errors, and
personal errors.
Random Error
Random error, also called indeterminate error, arises from the effects of uncontrolled (and
maybe uncontrollable) variables in the measurement. Random error has an equal chance of being
too high while others are too low (positive or negative). It is always present and cannot be
corrected. It affects the distribution of measurements around a central value and characterized by
a random variation in both magnitude and direction. Indeterminate errors can be traced to several
sources, including the collection of samples, the manipulation of samples during the analysis,
and the making of measurements. There is random error associated with reading a scale.
Although it is impossible to eliminate indeterminate error, its effect can be minimized if the
sources and relative magnitudes of the indeterminate error are known. Indeterminate errors may
be estimated by an appropriate measure of spread.

31
3.4 Confidence limit (interval)

From a limited number of measurements, we cannot find the true population mean, or the true
standard deviation, . What we can determine are X and s, the sample mean and the sample
standard deviation. The confidence interval is an expression stating that the true mean, is
likely to lie within a certain distance from the measured mean, X . The confidence interval of
is given by

, where s is the measured standard deviation, n is the number of

observations, and t is Students t,

3.5 Testing for significance

A significance test or hypothesis testing is designed to determine whether the difference
between two or more values is too large to be explained by indeterminate error. The first step in
constructing a significance test is to state the experimental problem as a yes or no question. A
null hypothesis and an alternative hypothesis provide answers to the question.
Null hypothesis (Ho) is a statement that the difference between two values can be explained by
indeterminate error; retained if the significance test does not fail.
The significance level ( value) is calculated by

One-Tailed and Two-Tailed Significance Tests

Consider the situation when the accuracy of a new analytical method is evaluated by analyzing a
standard reference material with a known . A sample of the standard is analyzed, and the
samples mean is determined.
Ho: X =
Two-tailed significance test- is a significance test in which the null hypothesis is rejected for
values at either end of the normal distribution.
One-tailed significance test- is a significance test in which the null hypothesis is rejected for

values at only one end of the normal distribution. or .

Comparison of results
When it is required to compare the results of two methods, or of two instruments applying the
same analysis method, or of two laboratories upon the same sample, it is essential to refer to

32
statistical tests. Two main families exist: parametric and nonparametric tests. The first supposes
that data are distributed according to a Normal law (on which the values in Students table are
based), while non-parametric tests are based on so-called robust statistics, less sensitive to
abnormal values.
One sample t test
To compare an experimental mean with a known value
In order to decide whether the difference between X and is significant,

, where X = sample mean, s = sample standard deviation and n =

sample size.
If texp > tcritical value, the null hypothesis is rejected and the alternative hypothesis is accepted
If texp < tcritical value, the null hypothesis is retained at the stated significance level

Comparison of two experimental means

The result of an analysis is influenced by three factors: the method, the sample, and the analyst.
The influence of these factors can be studied by conducting a pair of experiments in which only
one factor is changed. For example, two methods can be compared by having the same analyst
apply both methods to the same sample and examining the resulting means. In a similar fashion,
it is possible to compare two analysts or two samples.

Significance testing for comparing two mean values is divided into two categories depending on
the source of the data. Data are said to be unpaired when each mean is derived from the analysis
of several samples drawn from the same source.
Paired data are encountered when analyzing a series of samples drawn from different sources.
UNPAIRED DATA

Consider two samples, A and B, for which mean values, X A and X B and standard deviations,
sA and sB, have been measured. If A =B

------------------- (**)
The value of texp compared with a critical value t(, v) as determined by the chosen significance
level, , the degrees of freedom for the sample, v, and whether the significance test is one-tailed
or two-tailed.

33
It is unclear, however, how many degrees of freedom are associated with t(, v) since there are
two sets of independent measurements.
- If the variances s2Aand s2B are the same, then the two standard deviations can be factored
out of equation(**) and replaced by a pooled standard deviation, spool, which provides a
better estimate for the precision of the analysis.

The pooled standard deviation can be calculated by

, the degree of freedom= nA+nB-2

- If sA and sB are significantly different, however, then texp must be calculated

F test (Comparison of two variances)

It is important to compare the standard deviations, i.e. the random errors of two sets of data. As
with tests on means, this comparison can take two forms. Either we may wish to test whether
Method one is more precise than Method two (i.e. a one-sided test) or we may wish to test
whether Methods one and two differ in their precision (i.e. a two-sided test).
The F test tells us whether two standard deviations are significantly different from each other.
F is the quotient of the squares of the standard deviations:

We always put the larger standard deviation in the numerator so that F1.
The null hypothesis states that if there are no significant differences in the variances, then the
ratio must be close to 1. The number of degrees of freedom of the numerator and denominator
are n1-1and n2-1 respectively.
- If Fcalculated > Fcritical(table), the standard deviations are significantly different from each other
at the given significance level.
- If Fcalculated < Fcritical(table), There is no evidence at the chosen significance level to suggest
that the difference in precisions is significant.

34
Rejection criteria Q-test (or Dixon test)
On occasion, a data set appears to be skewed by the presence of one or more data points that are
not consistent with the remaining data points. Such values are called outliers. The most
commonly used significance test for identifying outliers is Dixons Q-test. It is statistical test for
deciding if an outlier can be removed from a set of data.
The null hypothesis is that the apparent outlier is taken from the same population as the
remaining data. The alternative hypothesis is that the outlier comes from a different population,
and, therefore, should be excluded from consideration.
The Q-test compares the difference between the suspected outlier and its nearest numerical
neighbor to the range of the entire data set. Data are ranked from smallest to largest so that the
suspected outlier is either the first or the last data point. The test statistic, Qexp, is calculated
using

If Qexp > Qcritical the value in question can be rejected

Exercise
1. A new gravimetric method is developed for iron (III) in which the iron is precipitated in
crystalline form with an organoboron cage compound. The accuracy of the method is checked
by analyzing the iron in an ore sample and comparing with the results using the standard
precipitation ammonia and weighing of Fe2O3. The results reported as % Fe for each analysis,
were as follows:
Test method 20.10 20.50 18.65 19.25 19.40 19.99

Reference method 18.89 19.20 19.00 19.70 19.40

a) What are the confidence intervals of the two methods?

b) Is there any significant difference between these methods?
c) Is/are there any outlier(s)?

35
CHAPTER FOUR
Solutions and their Concentrations
Type of solution
A solution is a homogeneous mixture of two or more substance with a uniform composition. It
may exist in gas, liquid, or solid state. It has two components. The solute is a substance being
dissolved which present in smaller amount. The solvent is the component in greater amount.
There is no boundaries separating its components since it exists as one phase.
Solutions can be divided into three by their capacity to dissolve a solute. A solution that contains
the maximum amount of a solute in a given solvent, at a specific temperature, is called a
saturated solution. Before the saturation point is reached, the solution is said to be unsaturated;
it contains less solute than it has the capacity to dissolve. A third type, a supersaturated
solution, contains more solute than is present in a saturated solution. Supersaturated solutions
are not very stable. The six type of solutions are shown on the table.

Different ways of expressing concentration

The concentration is a general measurement unit stating the amount of solute present in a known
amount of solution. There are several ways of expressing the concentration of a solution.

Name units Symbol

Molarity moles slute M

liters solution
Formality number FWs solute F
liters solution

36
 Normality number EWs solute N
liters solution
Molality mole solute m
Kg solvent

Weight % g solute
x100 %

solution
Volume % ml solute
x 100 %

solution
Weight-to-volume % g solute
x 100 %

solution
Parts-per million g solute ppm
x106
g solution

Parts-per billion g solute ppb

x109
g solution

PREPARATION OF SOLUTIONS
Preparing a solution of known concentration is perhaps the most common activity in any
analytical lab. The method for measuring out the solute and solvent depend on the desired
concentration units, and how exact the solutions concentration needs to be known. Pipettes and
volumetric flasks are used when a solutions concentration must be exact; graduated cylinders,
beakers, and reagent bottles suffice when concentrations need only be approximate.

Preparation of Stock solution

Stock solution is a solution of known concentration from which other solutions are prepared. It
is prepared by weighing out an appropriate portion of a pure solid or by measuring out an
appropriate volume of a pure liquid and diluting to a known volume. Exactly how this is done
depends on the required concentration units. A solution can be prepared from solid or liquid
state.
Preparation of solution from solid
To prepare solution from solid so we must know the concentration this will be prepared in a
certain volume.
M = n / V (L) , where n = w / M.wt

37
 M = w / M.wt V (L)

w = M M.wt V (L): Where, M: molarity; n: number of mole; V: volume in litter and

M.wt: molecular weight.

Preparation of solution from liquid

To prepare solution from liquid state, we must know the molarity for the substance to help us to
know density (D), purity (P)
10
=
.
Exercise
Describe how you would prepare the following three solutions:
a) 500 mL of approximately 0.20 M NaOH using solid NaOH
b) 1 L of 150.0 ppm Cu2+ using Cu metal
c) 2 L of 4% v/v acetic acid using concentrated glacial acetic acid.
Preparing Solutions by Dilution
Solutions with small concentrations are often prepared by diluting a more concentrated stock
solution. A known volume of the stock solution is transferred to a new container and brought to a
new volume. Since the total amount of solute is the same before and after dilution, we know that
Co x Vo = Cd x Vd
Where Co is the concentration of the stock solution, Vo is the volume of the stock solution being
diluted, Cd is the concentration of the dilute solution, and Vd is the volume of the dilute solution.
Again, the type of glassware used to measure Vo and Vd depends on how exact the solutions
concentration must be known.
Example
A laboratory procedure calls for 250 mL of an approximately 0.10 M solution of NH3. Describe
how you would prepare this solution using a stock solution of concentrated 14.8M of NH3.
Activity and activity coefficient
The true thermodynamic equilibrium constant is a function of activity rather than concentration.
The activity of a species, aA, is defined as the product of its molar concentration, [A], and a
solution-dependent activity coefficient,A.
A = [A]A
The equilibrium constant expressions for the reaction
38
 aA + bB cC + dD

(aC ) c (a D ) d
Kc
(a A ) a (a B ) b
For gases, pure solids, pure liquids, and nonionic solutes, activity coefficients are approximately
unity under most reasonable experimental conditions. Activity coefficients for ionic solutes,
however, depend on the ionic composition of the solution. It is possible, using the extended
DebyeHckel theory to calculate activity coefficients using equation

Where ZA is the charge of the ion, A is the effective diameter of the hydrated ion in nanometers,
is the solutions ionic strength, and 0.51 and 3.3 are constants appropriate for aqueous
solutions at 25 C.
From the DebyeHcke equation
- As ionic strength increases, the activity coefficient decreases. The ionic strength
approaches zero, the activity coefficient approaches a value of one.
- As the magnitude of the charge of the ion increases, the departure of its activity
coefficient from unity increases. Activity coefficients are smaller, and thus activity
effects are more important, for ions with higher charges and smaller effective diameters.
- The extended DebyeHckel equation provides reasonable activity coefficients for ionic
strengths of less than 0.1M.
Ionic strength () is a measure of the total concentration of ions in solution. The more highly
charged an ion, the more it is counted.

Where Ci is the concentration of the ith species and is its charge. The sum extends over all ions in
solution.
Example 1
Find the ionic strength of a) 0.10 M NaNO3 b) 0.01M Na2SO4 and c) 0.020 M KBr plus 0.010
M Na2SO4.

39
Example 2
Calculate the solubility of Pb(IO3)2 in a matrix of 0.020 M Mg(NO3)2.
Solution
We begin by calculating the ionic strength of the solution. Since Pb(IO3)2 is only sparingly
soluble, we will assume that its contribution to the ionic strength can be ignored; thus

Activity coefficients for Pb2+ and I are

giving an activity coefficient for Pb2+ of 0.43. A similar calculation for IO3 gives its activity
coefficient as 0.81.
The equilibrium constant expression for the solubility of PbI2 is
Ksp = [Pb2+][IO3-]2Pb2+(IO3-)2; Let [Pb2+] = x and [IO3-] = 2x
(x)(2x)2(0.45)(0.81)2 = 2.5x10-13
Solving for x gives a value of 6.0x105 or a solubility of 6.0 x105 mol/L. This compares to a
value of 4.0x105 mol/L when activity is ignored. Failing to correct for activity effects
underestimates the solubility of PbI2 in this case by 33%.
40