ANALYTICAL CHEMISTRY

TOPIC 3: ANALYTICAL TECHNIQUES

Chemists carry out a wide variety of monitoring roles such as analysing for drug residues and measuring the
concentrations of pollutants such as pesticides in the environment. Chemists are also employed to analyse
materials used or produced by many branches of industry, including pharmaceuticals, polymers, metal
production, and food preparation. In this topic students consider some of the more common means of
analysis, and undertake practical activities in measurement.

Subtopic 3.1: Volumetric Analysis

Key Ideas Intended Student Learning
Concentrations of solutes in solutions can be described Convert concentrations from one unit into
by using a number of standard conventions. another, for example, mol L1, g L1, %w/v, ppm,
ppb.
Knowledge of the mole ratios of reactants can be used Perform stoichiometric calculations when given
in quantitative calculations. the reaction equation and the necessary data.
A titration can be used to determine the reacting Describe the correct use of a volumetric flask, a
volumes of two solutions. pipette, and a burette.
Analysis of a variety of chemicals depends upon an Describe and explain the procedure involved in
understanding of quantitative aspects of chemical carrying out a titration, particularly rinsing
reactions, including acid–base and redox reactions. glassware and determining the end-point.
A titration can be used to determine the concentration Determine the concentration of a solution of a
of a solution of a reactant in a chemical reaction. reactant in a chemical reaction by using the
results of a titration.
Volumetric Analysis
1. Mole Concept.
(a) Equations give the ratio of reactants and products in a chemical reaction.
Example consider the reaction Fe2O3+ 3CO  2Fe + 3CO2
The ratio of atoms is Fe2O3 : CO : Fe : CO2 is 1 : 3 : 2 : 3
This is called the reacting mole ratio.
(b) A mole is a fixed number of particles 6.02 x 1023. This constant is called Avogadro’s Constant.
The mass of a mole of particles is called the molar mass (M), which is the gram equivalent of
the relative atomic (Ar) (or molecular (Mr)) mass of the particle.
Example M (C) = Ar(C) g = 12.01 g mol-1(2dp)
M(CO2) = M(C) + 2M(O) = 12.01 + 2x16.00 = 44.01 g mol-1
Note : When working out the molar mass, use all significant figures given in the data (usually
the Periodic Table). Rounding off should only occur at the answer stage.
m
n=
(c) To calculate the number of moles (n) M where m = mass (g)
M = Molar Mass (g mol-1)
2. Concentration Terms.
(a) Most chemical reactions that we use are in solution so we need to know the concentration of the
species in the solution. (Note a solution is a mixture of a solvent (a liquid that dissolves things)
and a solute (the solid that dissolves).
(b) Molar Concentration (c) is the number of moles per litre (molL-1)
n
c =
V c = molar concentration (molL-1)

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n = number of moles (mol)

V = volume (L)
(c) Mass Concentration (c) is the mass of solute per litre.
m
c =
V c = mass concentration (g L-1)
m = mass (g)
V = volume (L)
Mainly used in consumer products
(d) Percentage weight per volume (%w/v) is the mass of solute in grams per 100 mL of solution (g
100 mL-1).
m
%w/v = x 10 0
V %w/v = percentage weight per volume (g 100 mL-1)
m = mass (g)
V = volume (mL)
Mainly used in consumer products
(e) Parts per million (ppm) represents the mass of solute, measured in milligrams, present in 1.00
kilogram of solution. This is the unit of choice for solutes with very low concentrations such as
salts present in mineral waters or heavy metal pollutants.
m
c ( ppm ) =
V ppm = parts per million (mg L-1)
m = mass (mg)
V = volume (L)
(f) Parts per billion (ppb) represents the mass of solute, measured in micrograms ( g), present in
1.00 kilogram of solution. This mainly used for solutions containing trace quantities of solutes
such as found in large quantities of water.
1 g = 1 x 10-3 mg = 1x 10-6 g
m
ppb =
V ppb = parts per billion (g L-1)
m = mass (g)
V = volume (L)

EXERCISE 1
1. Calculate molar mass of:
(a) Sulfuric acid
(b) Sodium hydroxide
2. A solution contained 4.9 g of suphuric acid in 200 mL of solution.
Convert this to :
(a) A molar concentration (mol L-1)
(a) A mass concentration (g L-1)
3. The concentration of glucose in the blood of a person was determined by analysis to be 4.5 x 10 -3 mol
L-1.
Convert this concentration to:

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(a) A mass concentration (g L-1)

(a) A ppm concentration
4. The label on a bottle of spring water states that the water contains magnesium at a concentration of 4
mg L-1.
Given that the magnesium is present as Mg2+, convert this concentration to:
(a) A molar concentration (mol L-1)
(a) A %w/v concentration
5. A body deoderant solution contains aluminium chlorohydrate, Al 2(OH)5Cl.2H2O, at a concentration of
17.5 %w/v.
convert this concentration to:
(a) A mass concentration (gL-1)
(a) A molar concentration (mol L-1)
6. (a) The concentration of tartaric acid, C2H4(OH)2(COOH)2 in a sample of red wine was determined
to be 2.5 g L-1.
Convert this concentration to a molar concentration (mol L-1).
(b) In the same sample of wine the concentration of the compound dimethyl sulphide was
determined to be 120 ppb.
Convert this concentration to molar concentration (mol L -1).
1. Complete the following table to show how to interconvert between various concentrations
mol L-1  g L-1  ppm  ppb
%w/v
2. A solution of sodium hydroxide was made by dissolving 1.00 g of NaOH in water to give 2.00 L of
solution. Calculate the concentration of the solution in:
(a) mol L-1___________________________________________________________________
(a) g L-1_____________________________________________________________________
(b) %w/v____________________________________________________________________
(c) ppm_____________________________________________________________________
(d) ppb______________________________________________________________________

3. Stoichiometric calculations.
Stoichiometry is the area of chemistry that deals with quantities of substances consumed in chemical
reactions.
Steps in the solution of problems.
(1) Write a balanced equation for the reaction.
m
(2) Calculate the number of moles of one substance using either n = cV or n = M
(3) Use the mole ratio from the equation to determine the number of moles of the
required substance.
(4) Convert the required substance to the required form (m, c, V, etc)
Example question
The reaction of copper metal with an aqueous solution of silver nitrate is represented by the
following equation:
Cu(s) + 2AgNO3(aq)  Cu(NO3)2(aq) + 2Ag(s)

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(a) Calculate the mass (in grams) of silver formed when 5.0 g of copper metal is consumed in this
reaction.
(b) Calculate the volume (in mL) of 0.10 mol L -1 silver nitrate solution required to exactly react
with 5.0 g of copper metal.
Calculations:
(c) from the equation, the mole ratio of silver produced: copper consumed is 2:1
nAg 2
=
nCu 1
nAg produced =2 x nCu consumed
5 .0
nCu consumed = 63.55 = 0.0787 mol
nAg produced = 2 x nCu consumed = 2 x 0.0787 mol = 0.157 mol
mAg produced = nAg produced x MAg = 0.157 x 107.87 g = 17 g (2 sf)
(d) from the equation, the reacting mole ratio of silver nitrate: copper is 2:1
nAgNO 2
3
=
n Cu 1
n AgNO
3 required to react = 2 x nCu consumed
mCu 5 .0
nCu consumed = M Cu = 63.55 = 0.0787 mol
n AgNO
3 required =2 x nCu consumed =2 x 0.0787 mol = 0.157 mol
nAgNO
3
c AgNO 3=
V AgNO
from the expression 3

0. 157
V AgNO n AgNO
it follows that 3 required 3 = 0.01 L = 1.6 L (2sf)

EXERCISE 2
1. For each of (a) and (b) below, use the chemical equation to calculate the amount (in mol) of the first
reactant required to exactly react with the given amount of the second reactant.
(a) nitric acid with 0.025 mol of potassium hydroxide
HNO3(aq) + KOH(aq)  KNO3(aq) + H2O(l)

(b)
Fe2+
( aq) with 0.0015 mol of
MnO−4 (aq )

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Fe2+ + − 3+ 2+
( aq) + 8 H ( aq) + MnO4 (aq )  5 Fe( aq) + Mn( aq ) (aq) + 4H2O(l)

7. Sufficient lead nitrate solution is added to 25.0 mL of potassium iodide solution to precipitate all of
the iodide ions as lead iodide, according to the following equation:
Pb2+ −
( aq) + 2 I (aq)  PbI2(s)
3.65 g of lead iodide precipitate is formed.
(a) Calculate the mass of iodide ion in the original 25.0 mL of solution
(b) Calculate the concentration of iodide ion in the original 25.0 mL of solution
(i) in gL-1
(ii) in mol L-1

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8. For each of (a) and (b) below use the chemical equation to calculate the volume (in mL) of solution of
the first reactant required to exactly react with the given volume of solution of the second reactant.
(a) 0.200 mol L-1 hydrochloric acid with 21.4 mL of 0.200 mol L -1 sodium hydroxide solution:
HC1(aq) + NaOH(aq)  NaCl(aq) + H2O(1)
(b) acidified 0.050 mol L-1 KI solution with 18.4 mL of 0.010 mol L-1 potassium dichromate
solution:

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I −(aq) + 14 H(+aq) + Cr 2 O2− 3+
7(aq )  2 Cr(aq) + 3I2(aq) + 7H2O(l)

4. Stoichiometric calculations involving an excess of one reactant

When solutions of chemical reactants are mixed, one of two outcomes can result:
Either the mole ratio of the two reactants mixed will be the same as the reacting mole ratio as
shown in the chemical equation for the reaction. In this case, the two reactants will both be
entirely consumed.
Or the mole ratio of the two reactants mixed will not be the same as the reacting mole ratio as
shown in the chemical equation for the reaction. In this case, one of the reactants will be
entirely consumed and there will be a portion of the other reactant “left over” or “unreacted”.
The reactant that is entirely consumed is called the “limiting” reactant or reagent.
The reactant that is not entirely consumed is called the “excess” reactant or reagent.
Consider the following examples:
Example 1
100 mL of 0.10 mol L-1 CuSO4 solution is mixed with 50 mL of 0.40 mol L-1 NaOH solution. The
following reaction takes place:
CuSO4(aq) + 2NaOH(aq)  Cu(OH)2(s) + Na2SO4(aq)
Determine if there is an excess of one of the reactants and if so, the amount (in mol) of excess of this
reactant.
n(CuSO4) in the 100 mL of solution = c (CuSO4) x V = 0.10 x 0.100 mol = 0.010 mol
n(NaOH) in the 50 mL of solution = C(NaOH) x V = 0.40 x 0.050 mol = 0.020 mol
n(CuSO4) : n(NaOH) mixed = 0.010 : 0.020 = 1 : 2= reacting mole ratio
when the mole ratio of reactants mixed = the reacting mole ratio then both reactants are
entirely consumed in the reaction. Thus there is no excess reactant in this case.
Example 2.
200 mL of 0.10 mol L-1 H2O2 solution is mixed with 100 mL of 0.050 mol L-1 Na2SO3 solution. The
following reaction takes place:
H2O2(aq) + Na2SO3(aq)  Na2SO4(aq) + H2O(l)
Determine if there is an excess of one of the reactants and if so the amount (in mol) of excess of this
reactant.
n(H2O2) in the 200 mL of solution = c(H2O2) x V = 0.10 x 0.200 mol = 0.020 mol
n(Na2SO3)in the 100 mL of solution = nNa2SO4 x V = 0.10 x 0.050 mol = 0.0050 mol
n(H2O2) : n(Na2SO3) mixed = 0.020: 0.0050 = 4: 1
reacting mole ratio n(H2O2) n(Na2SO3) = 1 : 1
when the mole ratio of reactants mixed  the reacting mole ratio then both reactants are not
entirely consumed in the reaction. Thus one of the reactants is in excess.

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By comparing the mole ratio of reactants mixed with the reacting mole ratio it can be seen that the
H2O2 is in excess. All of the Na2SO3 is consumed and it is therefore the limiting reactant.
if the Na2SO3 is the limiting reagent then 0.0050 mol of Na2SO3 reacts it then follows from the
reacting mole ratio that 0.0050 mol of H2O2 reacts as 0.020 mol of H2O2 was added to the Na2SO3
solution initially it follows that -
0.020 mol - 0.0050 mol of H2O2 (= 0.015 mol H2O2) did not react
thus the excess amount of H2O2 was 0.015 mol
For calculations involving an excess of reagent the key steps are as follows:
1. Calculate the mole ratio of reactants mixed.
2. Compare the mole ratio of reactants mixed with the reacting mole ratio to determine which
reactant is in excess and thus which reactant is the limiting reactant.
3. Calculate the reacting quantities on the basis that all of the limiting reactant is consumed.

EXERCISE 3
1. 2.00 g of zinc metal was added to 100 mL of 0.10 mol L-1 copper nitrate solution. The following
reaction took place:
Zn(s) + Cu(NO3)2(aq)  Zn(NO3)2(aq) + Cu(s)
(a) Determine which reactant is present in excess and by how many mol.
(b) Calculate the number of mol of zinc nitrate formed. Hence calculate the concentration of zinc
nitrate (in mol L-1) in the solution at the end of the reaction.
(c) Calculate the mass of copper metal formed.
9. 50.0 mL of a solution containing 15.0 g of dissolved aluminium chloride, AlCl 3, was mixed with 50.0
mL of a solution containing 12.0 g of dissolved sodium hydroxide, NaOH.
The following reaction took place:
3NaOH(aq) + AlCl3(aq)  Al(OH)3(s)+ 3NaCl(aq)
Given that one of the reactants is in excess:
(a) Calculate the mass of aluminium hydroxide precipitate formed.
(a) Calculate the concentration of sodium chloride (in mol L-1 ) in the solution at the end of the
reaction.

5. Chemical Titrations.
There are three practical activities associated with Titrations:
1. preparation of solutions to be used in the titration
2. preparation of glassware to be used in the titration
3. performing the titration, including the recording of burette readings
At the conclusion of a titration, calculations must be performed using data obtained from the titration.
1. Preparation of solutions to be used in a titration
A titration determines the volume of a solution of one reactant needed to react with a
measured volume of a solution of the other reactant. The concentration of one of the
solutions must be accurately known, while the other solution (the solution being analysed) is
of unknown concentration. A solution of known concentration is called a standard solution.
It may be prepared by dissolving a known amount of solute in sufficient water to make an

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accurately known volume of solution, or it may be prepared by accurate dilution of a more

concentrated standard solution, referred to as a stock solution. In both procedures, a
volumetric flask is used for the accurate measurement of the volume of the solution. When a
standard solution is prepared by dissolving a measured mass of solute in water to make a
known volume of solution then it is known as a primary standard.
Preparing a standard solution from a primary standard
The substance selected as the primary standard must:
• react in some detectable way with the substance under analysis. For example, in
determining the concentration of an acid solution, a base is used because it reacts with acid.
• be available in pure form - called Analytical Reagent (AR) quality;
• be stable in air (not reactive towards carbon dioxide and oxygen) and in water;
• react only with the substance under analysis in the titration;
• be soluble in water.
As an example, sodium carbonate is used as a primary standard for determining the
concentration of an acid solution, because it meets all of the above criteria. Sodium
hydroxide is not used as a primary standard, because it readily absorbs water and carbon
dioxide from the atmosphere.
Preparing the solution

 Decide on the concentration and volume of standard solution required. By using the expression n
= c x V, calculate the number of moles of primary standard needed to produce the required
concentration and volume of solution. Then by using the expression m = n x M, calculate the
mass of primary standard needed.
 Use an electronic balance to accurately weigh out in a small beaker a mass of primary standard
(1) which approximates to the pre-calculated mass. Record this mass.
 Dissolve the primary standard in a minimum volume of distilled water in the beaker (optional -
the solid may be transferred directly to the volumetric flask).
 After washing the volumetric flask finally rinse it with distilled water. Transfer the solution, or
the dry solid, from the beaker to the volumetric flask via a funnel(2).
 Wash all traces of the solution or the solid from the funnel into the volumetric flask by rinsing
the beaker and funnel with distilled water from a wash bottle (3).
 Add more distilled water to the volumetric flask until the bottom of the meniscus is aligned with
the calibration mark. To ensure accuracy, use a teat pipette to add the final few millilitres of
water (4).

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 Stopper the flask and invert several times to mix the contents and thereby ensure the solution is
of uniform concentration throughout. Label the flask.

EXERCISE 4
Calculate the mass (in g) of solid sodium carbonate, Na2CO3, needed to make 200 mL of sodium carbonate
solution of concentration 0.050 mol L-1.

Preparing a standard solution by dilution of a more concentrated standard solution

 Decide on the concentration and volume of standard solution required. By using the expression n
= c x V, calculate the number of moles of solute needed to produce the required concentration
and volume of solution.
 By using the expression V = n/c, calculate the volume of the more concentrated standard
solution, needed to make the dilute standard solution.
 Transfer this volume of the more concentrated solution from a burette to a volumetric flask and
bring the solution to the required volume as described above. (The detailed procedure for
rinsing, filling and delivering from a burette are described below)

EXERCISE 5
Calculate the volume (in mL) of 2.00 mol L-1 hydrochloric acid that must be diluted to make 200 mL of 0.050
mol L-1 hydrochloric acid.

2. Preparation of glassware to be used in the titration

The key items of glassware used in a titration are a fixed volume pipette, a burette and a
conical flask that contains the solution being analysed. All glassware items must be firstly
washed in detergent solution, then rinsed with distilled water before finally rinsing as
follows:
Pipette - final rinsing is with the solution to be transferred in the pipette
Burette -final rinsing is with the solution to be delivered from the burette
Conical flask - final rinsing is with distilled water
3. Performing the titration
Determining the end point of a titration
The point in a titration at which just enough reactant has been delivered from the burette to
exactly react with the substance under analysis in the conical flask is called the equivalence
point of the titration. This point is detected either by the colour change of one of the
reactants or of a chemical indicator that has been added to the solution being analysed. It
may also be detected by using a meter, such as a pH meter (for acid-base titrations).
Effective chemical indicators are substances that change colour at or very close to the
equivalence point for a titration. The colour change needs to be sharp and easily detected by
the eye.
The point at which the indicator shows the first permanent colour change in the conical flask
is called the end point for the titration. Ideally the end point should exactly coincide with the
equivalence point. Sometimes in redox titrations a change in colour of one of the reactants
provides an indication that the end point has been reached. One common example of this is

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the purple-pink colour of permanganate that appears at the end point when permanganate
solution is being delivered from a burette into a solution containing a reducing agent.
Some common examples of chemical indicators.

Type of titration Indicator (in flask) Colour change

strong or weak base added to strong acid bromophenol blue yellow to blue
in flask
strong base added to weak acid in flask phenolphthalein colourless to pink
iodine solution added to a solution of a Starch colourless to blue
reducer
permanganate solution added to a no added indicator colourless to pink
colourless solution of a reducer
Using the pipette

Filling
 Fill the previously rinsed pipette to above the calibration mark (5) using a pipette filler.
 Remove the pipette from the solution and wipe off any liquid on the outside of the pipette using
a tissue.
 Carefully adjust the level in the pipette so that the bottom of the meniscus is aligned with the
mark when the pipette is held vertically and at eye level. Make sure there are no air bubbles in
the pipette (6).
Delivering
 Holding the pipette vertically and the receiving vessel (usually a conical flask, prerinsed with
distilled water) on an angle, touch the pipette tip on the wall of the flask and allow it to drain (7).
 Hold the tip of the pipette against the wall of the flask for 10 seconds (draining time),
remembering that a small volume of liquid is meant to remain in the pipette - do not blow it out.

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Adding the indicator solution.

 Add a small number of drops of an appropriate indicator solution, if needed, to the solution in
the conical flask.
Using the burette
Rinsing
 Rinse the burette, firstly with distilled water then with the solution to be placed in it, by placing a
funnel in the top of the burette and adding a small portion of the solution to the burette.
 Hold the burette with barrel horizontal and rotate about its main axis to ensure all the internal
surface is rinsed.
 Pass the rinsing liquid out through the tap.
Filling
 Close the tap and fill the burette with the solution. Ensure there are no air bubbles in the burette
and that the section of the burette below the tap is filled(8).
 Note the initial burette reading - read with the bottom of the meniscus aligned at eye-level(9),
estimating the second decimal place.
Delivering
 Add the solution slowly from the burette to the conical flask, swirling the flask to ensure
complete mixing
 When there is an indication that the end point is near (indicator colour takes a longer time to
change), slow down the addition to one drop at a time and after each drop, touch the tip of the
burette on the wall of the flask and rinse the drop into the solution with distilled water.
 Repeat this until a permanent colour change is achieved.
 Note the final burette reading. The difference between the initial and final burette readings is
called the titre value.
 Repeat the titration procedure until three concordant titre values (values within 0.1 mL of each
other) are obtained.

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Using the burette

ASSIGNMENT 3.1 : VOLUMETRIC ANALYSIS
[Given:Avogadro's Constant = 6.0221415 × 1023 mol-1]
1. (a) What is the mass of 0.020 mole of thorium atoms?
(b) What is the mass of 2 mole of nickel atoms?
(a) How many mole of substance are in each of the following?
(i) 32 g of sulfur molecules S8
(ii) 0.250 g of sulfur dioxide
(iii) 3.01 x 1024 molecules of SO2
6. What mass of each of the following is dissolved in 250 mL of 0.100 mol L-1solution?
(a) Silver nitrate
(b) potassium permanganate
(c) sodium thiosulfate Na2S2O3.5H2O
7. Calculate the amount of solute (mol) contained in the following solutions.
(a) 0.100 L of 0.1 00 mol L-1 silver nitrate
(b) 25 mL of 2.00 mol L-1sodium chloride
(c) 12.2 mL of 1.56 mol L-1sulfuric acid.
8. Calculate the molar concentration of the following solutions:
(a) 3.16 g of potassium permanganate (KMnO4) in 2.00 L of water.
(b) 5.62 g of hydrated copper (II) sulfate CuSO4.5H2O in 250 mL of solution.
9. How many mL of 0.480 mol L-1 sulfuric acid is required to neutralize 26.0 mL of 0.612 mol L-1 sodium
hydroxide?
10. What is the molar concentration of a solution of sulfuric acid if 42.7 mL is required to exactly titrate
27.5 mL of 0.612mol L-1 sodium hydroxide?
11. Some solid anhydrous sodium carbonate completely reacts with 20.0 mL of 0.250mol L -1 hydrochloric
acid. Find the mass of sodium carbonate reacted.
12. To reclaim silver salts, silver precipitates are converted to silver oxide by a series of reactions. Silver
nitrate can then be prepared when needed by adding nitric acid to the oxide.
Ag2O + 2HNO3  2AgNO3+H2O
Calculate the mass of silver oxide and the volume of 2.0 mol L-1nitric acid which must be mixed to
produce 1.0 litre of 0.10mol L-1 silver nitrate.
13. One litre of a potassium hydroxide solution was prepared by dissolving 4.9 g in pure water. A
titration against an unknown acid was performed and 20.0 mL of alkali were required to neutralize
25.0 mL of acid. Calculate the concentration of
H(+aq) in the acid.

14. A household cleanser advertises, “contains 33% of real ammonia” - for greater cleaning power of
course! To test this claim, a titration was done. 16 mL of 0.50 mol L-1 HCl(aq) were required to
neutralize 1.0 mL household ammonia. Comment on the claim made.
15. One gram of an acid HA of unknown formula is dissolved in water and 20.72 mL of 0.588 mol L -1
sodium hydroxide solution is added.
HA(aq) + NaOH(aq)  NaA(aq) + H2O
-1
7.82 mL of 0.510 mol L hydrochloric acid is required to neutralize the excess hydroxide. What is the
molar mass of HA?

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16. 0.930g of a hydrated form of sodium carbonate reacts exactly with 150 mL of 0.100mol L -1
hydrochloric acid. Calculate the number of molecules of water of crystallisation present. (i.e. if the
formula of the carbonate is Na2CO3.xH2O find x)

Subtopic 3.2: Chromatography

Key Ideas Intended Student Learning
Adsorption chromatography involves the use of a Identify the stationary and mobile phases in an
stationary phase and a mobile phase to separate the adsorption chromatography process.
components of a mixture.
The strength of attraction between two substances Predict the relative strengths of attraction of
depends upon their relative polarities. components for the stationary phase and the
mobile phase on the basis of their polarities.
The rate of movement of any component along a Predict the relative rates of movement of
stationary phase is determined by the structure or components along a stationary phase, given the
relative polarity of the component and the relative structural formulae or relative polarities of the
polarities of the stationary phase and the mobile components and the two phases.
phase.
The rate of movement of a component along a Describe and apply RF values and retention times
stationary phase is compared with a known standard in the identification of components in a mixture.
in order to identify the component.
CHROMATOGRAPHY
Chromatography is a method used to separate and or to analyze complex mixtures. The components to be
separated are distributed between two phases: a stationary phase bed and a mobile phase which percolates
through the stationary bed. A mixture of various components enters a chromatography process, and the
different components are flushed through the system at different rates. These differential rates of migration
as the mixture moves over adsorptive materials provide separation. Repeated sorption/desorption acts that
take place during the movement of the sample over the stationary bed determine the rates. The smaller the
affinity a molecule has for the stationary phase, the shorter the time spent in a column.
Importance
Chromatography can separate complex mixtures with great precision. Even very similar components, such as
proteins that may only vary by a single amino acid, can be separated with chromatography. In fact,
chromatography can purify basically any soluble or volatile substance if the right adsorbent material, carrier
fluid, and operating conditions are employed. Second, chromatography can be used to separate delicate
products since the conditions under which it is performed are not typically severe. For these reasons,
chromatography is quite well suited to a variety of uses in the field of analysis.
Adsorption
Adsorption is the attachment of molecules to the surface of a solid. The attachment occurs when secondary
bonds form between the molecules and atoms at the surface of the solid. Those molecules that form stronger
secondary bonds with the surface atoms are more strongly adsorbed to the surface. Note absorption occurs
when the molecules are absorbed into material.

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Adsorption Chromatography
There are several forms of adsorption chromatography, but they are all based on the principle of different
rates of movement of each component of the mixture through a solid called the stationary phase. The
components are transported through the stationary phase by a liquid called the mobile phase. The rate of
movement of each component is dependent on the strength of its bonds with the surface of the stationary
phase relative to the strength of its bonds with the mobile phase.
The separation process in adsorption chromatography
A sample of the mixture to be separated is brought into contact with the surface of the stationary phase over
which a liquid (or gaseous) mobile phase is allowed to flow.
The components of the mixture are adsorbed onto the surface of the stationary phase (see Diagram A,
below). At the same time, the mobile phase bonds, with varying degrees of strength, with the different
components of the mixture and carries them along with it (see Diagram B, below). The attachment of the
particles of the mixture's components to the stationary and mobile phases is usually by secondary bonding.
Each component of the mixture will display a different tendency to be adsorbed onto the stationary phase
surface and to be carried along by the mobile phase. The polarity of the component molecule relative to the
polarities of the mobile phase molecules and the stationary phase material determine the extent of these
differing tendencies. This results in different rates of movement of the components along the stationary
phase surface. Separation is thus achieved (see Diagram C, below).
Components that are strongly adsorbed onto the surface of the stationary phase and weakly bonded with the
mobile phase will hardly move from the original point of contact with the stationary phase. The components
that are more soluble in the mobile phase will move further along the surface in a given time (see Figure
below).
For normal phase chromatography, the more polar components bond more strongly with the polar stationary
phase and their movement in the direction of the flow of the mobile phase is more severely retarded.
It is important to choose the appropriate adsorbent and solvent system to give the best separation for a
particular mixture. If a non-polar solvent was chosen for the separation of a mixture of polar substances, the
mixture would remain at the origin and no detectable separation would result.

13
 ANALYTICAL CHEMISTRY

The
adsorption chromatography process
In adsorption chromatography, small differences in the adsorption-desorption behaviour of substances for a
combination of a particular liquid or gas mobile phase with a particular solid stationary phase are used to
achieve a separation.
Particle interacts strongly
with the solvent
Direction of
movement of Mobile phase
the solvent
(mobile phase)
Stationary phase

Particle is adsorbed strongly

onto the surface of the
stationary phase

The Retardation Factor

For a given mobile phase-stationary phase combination the movement of any component relative to the
solvent is reproducible and can be used for identification. The movement of any compound is most
conveniently expressed as its retardation factor value, Rf.
Retardation factor value for a compound is defined as the ratio of the distance that the spot of a particular
compound on the thin layer chromatography plate is from the baseline relative to the distance moved by the
solvent front.
distance moved by compound (from baseline )
Rf =
distance moved by solvent ( from baseline )

14
 ANALYTICAL CHEMISTRY

Example

Solvent front
7
Rf ( A )= =0 .7
10

8
Rf ( B)= = 0. 8
10

10 cm 2
Rf ( C )= =0 . 2
10
8 cm
7 cm

2 cm

origin
A B C

Each component has a unique retardation factor and it can be used to identify components
Other types of chromatography
Gas-solid chromatography
Liquid-solid chromatography
ASSIGNMENT 3.2: CHROMATOGRAPHY
1. Chromatography is an important way to separate of mixtures.
(a) What is the difference between adsorption and absorption?
(b) Distinguish between the stationary phase and the mobile phase in an adsorption
chromatography process.

15
 ANALYTICAL CHEMISTRY

17. Given the following chromatogram.

Solvent front

9 cm

7.5 cm
6.5 cm

2.5 cm

origin
A B C

(a) Which component is more strongly attracted to the solvent?

(b) Given that the solvent is water, and the components have general formulae ROH, RCOOH and
RCHO.
(i) Give the general names of the components.
(ii) Predict which formula goes with which spot.
(iii) Explain your reasoning in the previous question.
(c) Which component forms stronger secondary bonds with the stationary phase?
(d) Calculate the Rf values for components A, B and C
(e) How far would each spot have moved if the solvent front had moved up 6 cm from the origin
instead of 9 cm?
18. Separate samples of three amino acids, A, B and C, were spotted on the base line of a thin layer
chromatography sheet. The chromatogram produced using a particular mobile phase is shown below.

Amino acid Rf value

Alanine 0.56
Arganine 0.61
Isoleucine 0.82
Proline 0.89
Taurine 0.34
Valine 0.75

(a) By means of suitable measurements and calculations and then using the table of R f values,
identify A, B and C.
(b) Where would you expect valine and proline spots to be on this chromatogram.
19. What is meant by

16
 ANALYTICAL CHEMISTRY

(a) Gas-solid chromatography

(b) Liquid-solid chromatography
20. Ethanal in the body leads to the production of an altered form of the base guanine.
The presence of the altered base can be detected by chromatography.

A mixture of the four normal DNA bases may be separated by liquid chromatography, using a polar
solvent on a non-polar stationary phase. One chromatogram is shown in the diagram below:
(a) Which base spends the least time in the chromatograph?
(b) Which base is most strongly bond to the solvent?
(c) Explain how the chromatogram indicates that cytosine is the most polar base.
(d) State how the presence of an altered form of the base guanine in a mixture of DNA bases would
change the appearance of this chromatogram.

Subtopic 3.3: Atomic Spectroscopy

Key Ideas Intended Student Learning
Electrons move to a higher or lower energy level when State the effect of absorption or emission of
atoms or ions absorb or emit radiation. radiation on the energy levels of electrons in
atoms or ions.
The wavelengths of radiation emitted and absorbed by State that the wavelengths of radiation emitted
an element are unique to that element. and absorbed by an element are unique to that
element.
The wavelengths of radiation absorbed by an element Explain the principles of atomic absorption
can be used to identify its presence in a sample. spectroscopy in identifying elements in a sample.
Atomic absorption spectroscopy is used for Describe the construction and use of calibration
quantitative analysis. graphs in determining the concentration of an
element in a sample.
1. Emission Spectra
When metal salts are heated in a flame characteristic colours are given off – Flame Colours
The same colours are produced in high voltage discharge tubes (eg sodium vapour lamps)
When light is passed through a spectrometer (prism or diffraction grating) a series of coloured lines on
a black background are produced – a line emission spectrum
Each element has its own unique spectrum and can be used for identification.

17
 ANALYTICAL CHEMISTRY

Production of the spectrum

Electrons exist in energy levels and tend to send up in the lowest energy level/ When given energy (in
the form of heat, light or electricity) electrons will jump to higher energy levels. They are unstable in
this state and rapidly fall back to the lowest energy level available, giving off this energy as
electromagnetic radiation in the process.
Excited energy state

Energy out as the

Electron jumps electron falls back to
energy levels its lowest energy state

Lowest energy state

Energy in

Absorption Spectra
White light is made up of all the colours of the spectrum. When white light passes through a vapour of
a metal, some wavelengths of the radiation are absorbed, and excite electrons to higher energy states.
This energy is lost almost immediately as electromagnetic radiation but in all directions, so the
emerging beam is minus that radiation. This produces a spectrum minus some colours – an
Absorption spectrum.

Atomic absorption spectroscopy (AAS)

AAS involves the absorption of electromagnetic radiation of specific wavelengths (or frequencies) by
a sample to be analysed.
A spectrophotometer is used to analyse the sample.
The only wavelength absorbed is that of the element being tested. This means that the presence of
other elements does not affect the results.
Requirements
 A source of radiation (of a particular wavelength), usually a lamp containing the metal to be tested
for.
 A sample sprayed (or aspirated) into a flame.

18
 ANALYTICAL CHEMISTRY

 A detector

Flame

Lamp detector
Linear burner (10 cm)

Sample introduced into the

flame

The intensity of the incident beam (I0) and transmitted beams (It) are measured and used to calculate
the absorbance (A). The Absorbance (A) is defined as
I
A= log 0
It
To measure the concentration of a particular element, a calibration curve must be used. Solutions of
known concentration are measured and graphed.
Absorbance

concentration

The absorbance of the sample is measured and compared to the calibration curve to determine its
concentration.
EXERCISE 3.3: ATOMIC ABSORPTION SPECTROSCOPY
1. An atom or ion gives out light when exposed to radiation.
(e) Explain why.
(f) Describe the resulting spectrum if the light is passed through a spectrometer.
(g) How can different elements be distinguished from each other using this spectrum?
21. When white light passes through a gas containing ions light is absorbed.
(a) Explain why light is absorbed.
(b) Describe the spectrum produced when this light is passed through a spectrometer.
(c) Explain how this is used in atomic absorption spectroscopy (AAS).
22. How can AAS be used to identify elements?

19
 ANALYTICAL CHEMISTRY

23. How can AAS be used to measure the concentration of atoms or ions in a sample?
24. A home grown tomato was tested for the amount of lead present by atomic absorption spectroscopy
AAS) to be certain that it was below the recommended concentration of 2.5 ppm. Standard solutions
were first run to obtain a calibration graph. The results are shown in the table below.
standard solution absorption
concentration(ppm)
0 0.02
0.10 0.57
0.20 1.12
0.30 1.67
0.40 2.22
0.50 2.77

A 20.0 g sample of the tomato was then taken and dissolved in 100 ml of nitric acid. This solution was
then tested for lead using the atomic absorption spectroscope and an absorption reading of 1.43 was
obtained.
(a) Plot the calibration graph.
(b) Determine the concentration in ppm of the diluted solution.
(c) Determine the concentration of lead (in ppm) in the tomato and state whether it was 'safe' to
eat.
(d) Lead is often associated with other heavy metals such as cadmium, mercury, arsenic as well as
zinc. Explain why cadmium can be quantitatively analysed, without interference from the other
metal ions present in the sample, by atomic absorption spectroscopy.
25. Lead pollution is a problem involving air, water and soil. While the average lead content of the earths
crust is 16 ppm levels of several thousand ppm can be found near smelters. A sample of water is
analysed using AAS and its absorbance recorded. A set of standard solutions, of varying
concentrations of lead is also analysed, the results are shown below.
standard solution concentration absorption
-1
(mg L )
0.000 0.000
0.005 0.037
0.010 0.079
0.020 0.137
Water Sample 0.110
(a) Construct a calibration curve from the above data.
(b) Using your calibration curve determine the lead concentration of the water sample.
(c) Convert your answer from mg L-1 to parts per million.
(d) If you drank a glass of this water (300 mL), calculate the mass of lead that you would have
ingested.
(e) Atomic absorption spectroscopy is a technique that can be used for both qualitative and
quantitative analyses. Explain the meaning of the terms qualitative and quantitative analysis.

20
 ANALYTICAL CHEMISTRY

ASSIGNMENT 3.1 :VOLUMETRIC ANALYSIS ANSWERS

1. (a) n = 0.02 mol
M(Th) = 232.0 g mol-1
m = nM = 0.02 x 232 = 4.62 g = 4.6 g (2 sf)
(b) n = 2 mol
M(Ni) = 58.70
m = nM = 2 x 58.70 =117.4 g = 100 g (1 sf)
(a) (i) m(S8) = 32 g
M(S8) = 32.06 x 8 = 256.48 g mol-1
m 32
n( S )= = =0 . 124766=0 . 12 mol( 2sf )
M 256 . 48
(ii) m(SO2) = 0.250 g
M(SO2) = 32.06 + 2 x16.00 = 64.06 g mol-1
m 0 . 250
n( SO 2 )= = =3 . 90259. . x 10−3 =3 . 90 x 10−3 mol( 3sf )
M 64 . 06
(i) N(SO2) = 3.01 x 1024 molecules
L = Avogadro’s constant = 6.02 x 1023 mol-1
N 3 . 01 x 1024
n( SO 2 )= = =5 .00 mol
L 6 . 02 x 1023
V = 250 mL = 0.250 L, C = 0.100 mol L-1, n = cV = 0.100 x 0.250 = 0.0250 mol
M(AgNO3) =107.9 + 14.01 + 3 x 16.00 = 169.91 g mol-1
m = nM = 0.0250 x 169.91 = 4.24775 = 4.25 g (3 sf)
(b) M(KMnO4) =39.10 + 54.94 + 4 x 16.00 = 158.04 g mol-1
m = nM = 0.0250 x 158.04 = 3.951 = 3.95 g (3 sf)
(c) M(Na2S2O3.5H2O) =2 x 22.99 + 32.06 x 2 + 3 x 16.00 + 5(2 x 1.008 + 16) = 248.18 g mol-1
m = nM = 0.0250 x 248.18 = 6.2045 = 6.20 g (3 sf)
(a) n = cV = .100 x 0.100 = 0.0100 mol (3sf)
(b) n = cV = 2 x 0.025 = 0.050 mol (2sf)
(d) n = cV = 1.56 x 0.0122 = 0.019032 = 0.0190 mol (3sf)
(a) m = 3.16 g, M(KMnO4) = 158.04 g mol-1, V = 2.00 L
m 3 .16
n= = =0 .0199949 mol
M 158 .04
n 0. 0199949
c= = =0 . 0099975= 0. 0100 mol L−1
V 2. 00
(b) m = 5.62 g, M(CuSO4.5H2O)) = 249.69 g mol-1, V = 250 mL = 0.250 L
m 5. 62
n= = =0 . 0225079 mol
M 249 .69
n 0. 0225079
c= = =0 . 0900316= 0 .0900 mol L−1
V 0. 250

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 ANALYTICAL CHEMISTRY

H2SO4 + 2NaOH  Na2SO4 + 2H2O

c(NaOH) = 0.612 mol L-1, V(NaOH) = 26.0 mL = 0.026 L, n = cV = 0.612 x 0.026 = 0.015912 mol
c(H2SO4) = 0.480 mol L-1
n( H 2 SO 4 ) 1
=
n ( NaOH ) 2
1 1
n(H2SO4) = 2 x n (NaOH) = 2 x 0.015912 = 0.007956 mol
n 0. 007956
= =0 . 016575= 16. 6 mL ( 3 sf )
v(H2SO4) = c 0 . 480
H2SO4 + 2NaOH  Na2SO4 + 2H2O
c(NaOH) = 0.612 mol L-1, V(NaOH) = 27.5 mL = 0.0275 L, n = cV = 0.612 x 0.0275 = 0.01683 mol
c(H2SO4) = 42.7 mL = 0.0427 L
n( H 2 SO 4 ) 1
=
n ( NaOH ) 2
1 1
n(H2SO4) = 2 x n (NaOH) = 2 x 0.01683 = 0.008415 mol
n 0 . 008415
= =0 .1970726=0 . 197 mol L−1 ( 3 sf )
c(H2SO4) = V 0 . 0427
Na2CO3 + 2HCl  2NaCl + CO2 + H2O
c(HCl) = 0.250 mol L-1, V(HCl) = 20.0 mL = 0.0200 L, n = cV = 0.250 x 0.0200 = 0.00500 mol
M(Na2CO3) = 22.99 x 2 + 12.01 + 3 x 16.00 = 105.99 g mol-1
n( Na2 CO 3 ) 1
=
n( HCl) 2
1 1
n(Na2CO3) = 2 x n (HCl) = 2 x 0.00500 = 0.00250 mol
m(Na2CO3) = nM = 0.0025 x 105.99 = 0.264975 = 0.265 g (3sf)
To reclaim silver salts, silver precipitates are converted to silver oxide by a series of reactions. Silver nitrate can then be
prepared when needed by adding nitric acid to the oxide.
Ag2O + 2HNO3  2AgNO3+H2O
Calculate the mass of silver oxide and the volume of 2.00 mol L-1nitric acid which must be mixed to produce 1
litre of 0.10 mol L-1 silver nitrate.

V(AgNO3) = 1L n( Ag 2 O ) 1
=
c(AgNO3) = 0.10mol L-1 n( AgNO 3 ) 2

n(AgNO3) = cV = 0.10 x 1 = 0.10 mol

1
n (Ag2O) = 2 n(AgNO3)
M(Ag2O) = 107.9 x 2 + 16.0
1
= 231.8 g mol-1
= 2 x 0.10 = 0.05 mol
c(HNO3) = 2.00 mol L-1
m (Ag2O) = nM = 0.05 x 231.8
= 11.59
m (Ag2O) = 12 g (2sf)
n( HNO 3 ) 2 1
= =
n( AgNO 3 ) 2 1
n(HNO3) = n(AgNO3)
= 0.10 mol

22
 ANALYTICAL CHEMISTRY

n 0.10
V(HNO3) = c = 2.00
V(HNO3) = 0.05 L
V(HNO3) = 50 mL
One litre of a potassium hydroxide solution was prepared by dissolving 4.9g in pure water. A titration against an
unknown acid was performed and 20.0 mL of alkali were required to neutralize 25.0 mL of acid. Calculate the

concentration of
H+
( aq) in the acid.

V(KOH) = 1L H(+aq) K+
KOH +  (aq ) + H 2O
m(KOH) = 4.9 g
n(KOH) = cV
M(KOH) = 39.1 + 16.0 + 1.0
= 0.087344... x 0.020
= 56.1 g mol-1
= 0.001746 mol
m 4.9 +
n( H ) 1
n(KOH) = M = 56.1 =
n( KOH) 1
= 0.087344... mol
n(
H(+aq) ) = n(KOH)
n 0.08734
1 = 0.001746 mol
c(KOH) = V =
n 0. 0017468
= 0.08734 mol L-1 +
H(aq)
c( ) = V = 0. 025
V(KOH) = 20 mL = 0.020 L
= 0.069875
V(H+) = 25 mL = 0.025 L +
c(
H(aq) ) = 0.0700 mol L-1(3sf)
A household cleanser advertises, “contains 33% of real ammonia” - for greater cleaning power of course! To test this
claim, a titration was done. 16 mL of 0.50 mol L-1 HCl(aq) were required to neutralize 1.0 mL household
ammonia. Comment on the claim made.
V(HCl) = 16 mL = 0.016 L HCl + NH3  NH4Cl
c(HCl) = 0.50 mol L -1 n( NH3 ) 1
=
n(HCl) = cV = 0.50 x 0.016 n( KOH) 1

= 0.008 mol n(NH3) = n(HCl)

M(NH3) = 14.0 + 3 x 1.0 = 0.008 mol

= 17.0 g mol-1 m(NH3) = nM = .008 x 17.0

V(NH3) = 1.0 mL = 0.0010 L = 0.136 g

m
x 100
%wv = V ( mL)
0. 136
x 100
= 1 = 13.6
%wv = 14% (2sf) (a bit low unless the
ammonia is in the form of NH4OH)
One gram of an acid HA of unknown formula is dissolved in water and 20.72 mL of 0.588mol L-1 sodium hydroxide
solution is added.
HA(aq) + NaOH(aq)  NaA(aq) + H2O
7.82mL of 0.510 mol L-1 hydrochloric acid is required to neutralize the excess hydroxide. What is the molar
mass of HA?
m(KA) = 1g HCl + NaOH  NaA + H2O
V(NaOH) = 20.72 mL = 0.002073 L

23
 ANALYTICAL CHEMISTRY

c(NaOH) = 0.588 mol L-1 n(HCl ) 1

=
n(NaOH) = cV = 0.588 x 0.02073 n( NaOH) 1
= 0.01218924 mol n(NaOH)excess = n(HCl)

V(HCl) = 7.82 mL = 0.00782 L n(NaOH)reacted with HA = n(NaOH) – n(HCl)

c(HCl) = 0.510 mol L-1 = 0.01218924 - 0.0039882

n(HCl) = cV = 0.510 x 0.00782 = 0.00820104 mol

= 0.0039882 mol HA(aq) + NaOH(aq)  NaA(aq) + H2O

n( HA ) 1
=
n( NaOH) 1
n (HA) = n(NaOH)
= 0.00820104 mol
m 1
M(HA) = n = 0. 00820104 =
121.9
M(HA) = 122 g mol-1(3sf)
0.930g of a hydrated form of sodium carbonate reacts exactly with 150 mL of 0.100 mol L-1 hydrochloric acid.
Calculate the number of molecules of water of crystallisation present. (i.e. if the formula of the carbonate is
Na2CO3.xH2O find x)
V(HCl) = 150 mL = 0.150 L 2HCl + Na2CO3  2NaCl + CO2 +H2O
c(HCl) = 0.100 mol L-1 n( Na 2 CO 3 ) 1
=
n(HCl) = cV = 0.100 x 0.150 n( HCl) 2
1 1
= 0.0150 mol
n(Na2CO3) = 2 n(HCl) = 2 x 0.0150
M(Na2CO3) = 2 x 23.0 + 12.0 + 3 x 16
= 0. 0075mol
= 106.0 g mol-1
m(Na2CO3) = nM = .0075 x 106.0
M(H2O) = 2 x 1.0 + 16
= 0.795 g
= 18.0 g mol-1
m(H2O) = 0.930 - 0.795
= 0.135 g
m
n (H2O) = M
0. 135
= 18
= 0.0075 mol
n (H 2 O ) 0. 0075 1
n(Na 2 CO 3 ) = 0. 0075 = 1
x = 1
ASSIGNMENT 3.2 : CHROMATOGRAPHY ANSWERS
1. (a) Adsorption occurs when the solute molecules stick to the stationary phase while during absorption the
molecules are absorbed into the stationary phase.
(b) The stationary phase is the medium over which the solution moves, while the mobile phase is the moving
solution.
(a) B

24
 ANALYTICAL CHEMISTRY

(b) (i) ROH –alcohol, RCOOH – carboxylic acid, RCHO – aldehyde,

(ii) ROH – A, RCOOH – B, RCHO - C
(ii) RCOOH is the most polar molecule and dissolves best in water and moves furthest, while RCHO
is the least soluble.
(f) RCHO is the most likely to have the strongest bond to the stationery phase.
s( A ) 6 .5
Rf ( A ) = = =0 .72( 2sf )
(g) s( mobile ) 9
Rf(B) = 0.83 (2 sf)
Rf(C) = 0.28 (2 sf)
6.5
s ( A )= Rf ( a ) xs( solvent )= x 6= 4 . 3 cm
(h) 9
s(B) = 5.0 cm (2 sf)
s(C) = 1.7 cm (2 sf)
(a) Rf(A) = 0.78 (Valine)
Rf(A) = 0.33 (Taurine)
Rf(A) = 0.56 (alanine)
(b) Valine would be at A, proline would be 4.0 cm up from the origin.
(a) Gas-solid chromatography is when the unknown is added to a stream of gas passing through a stationary phase,
which is a column of permeable particles.
(b) Liquid-solid chromatography is when the unknown is added to a stream of liquid passing through a
stationary phase, which is a column of permeable particles.
(a) Cytosine – lowest retention time
(b) Cytosine – lowest retention time, therefore most strongly stuck to solvent
(c) Cytosine is most polar base because it is the base most strongly bonded to the polar solvent/mobile phase.
(i) The presence of guanine would change the chromatogram by increasing the area underneath the guanine
section of the chromatogram.
EXERCISE 3.3 ANSWERS : ATOMIC ABSORPTION SPECTROSCOPY
1. (a) When an atom or ion is hit with radiation, an electron absorbs a fixed amount of energy and jumps to a
higher energy level where it is unstable, so it falls back to the lower level releasing this energy as
electromagnetic radiation of a given frequency (h = hv).
This produces a line emission spectrum which consists of a series of bright coloured lines against a black
background.

(b) As the energy levels associated with each atom or ion are unique, the spectra produced are unique for
each atom (or ion).

(a) As white light contains a wide range of radiations, it has one frequency which has energy exactly equal to the
energy gap of the atom (or ion) and so the energy is absorbed as an electron jumps to a higher energy
level.
The resulting spectrum consists of a continuous spectrum with black (absorption) lines through it.
(b) In atomic absorption spectroscopy (AAS) a beam of light of particular frequency is passed through a gas
containing the ions to be tested and its absorbance is tested. The source of the light is a discharge tube
containing the same atoms or ions that are to be tested for, so the frequency of the light given out is the
same as that absorbed by the atoms or ions that are in the test gas.

25
 ANALYTICAL CHEMISTRY

(j) Since the light used comes from the same atoms as those that are to be tested, it can be used to test for a
unique element or ion.
(k) The absorbance of the elements is measured at various known concentrations and a calibration curve
constructed. Then the absorbance of the sample is tested and compared to the calibration curve to
determine the concentration of the unknown solution.
(a)

absorption vs concentration

2.5
Absorption

1.5

0.5

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Concentration (ppm)

(b) Concentration = 0.253 ppm in the diluted solution.

(c) Concentration = 0.253 x 5 = 1.26 ppm in the tomato. This is a safe level (<2.5ppm)
(d) Provided that a cadmium discharge tube is used as a source of light, it can be used to analyse for
cadmium, because none of the other metals absorb cadmium radiation.
(a)

absorption vs concentration

0.16
0.14
0.12
Absorption

0.1
0.08
0.06
0.04
0.02
0
0 0.005 0.01 0.015 0.02 0.025
-1
Concentration (mg L )

(b) The lead concentration of the water sample = 0.016 mg L -1.

(c) 0.016 mg L-1 = 0.016 ppm.
(d) m(Pb) = cV = 0.016 x 0.3 = 0.005 mg
(e) Qualitative analysis, shows the presence of a particular substance.
Quantitative analysis gives the amount of the substance.

26