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DEPARTMENT OF CHEMICAL ENGINEERING TECHNOLOGY

CHET 307
ANALYTICAL CHEMISTRY

FINAL THEORY EXAMINATION–FIRST SEMESTER (2011-2012G)

Time Allowed: 3 hours Maximum Marks: 35

Name:--------------------------------- Regn.No------------------- Section #---------

PLEASE READ THE FOLLOWING INSTRUCTIONS CAREFULLY

1. Write your name and I.D number in the space provided above
2. No support material written or printed is allowed in the examination hall/room
3. You may use only non-programmable calculators.
4. Do not use pencils for answering.
5. Answer all questions.
6. Use of dictionaries of any kind is NOT ALLOWED

Category Marks allotted Marks obtained

Part A ( Q1-Q5) 10
Part B (Q1-Q15) 15
Part C (Q1-Q20) 10
Total 35

PART – A

Instructor: Dr. E.P.JAGADEESH Date: 1 January 2012

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

Each question carries 2 Marks

1. Draw a neat diagram of a gas chromatograph and describe its functioning?

Ans: The important parts of a GC are: Injection Port, Column, Detector and Oven. The
sample is injected at the injection port where it get volatilized and carried to the column
then by the carrier gas. The column separates the components depending on the
affinities of them to the column material and the carrier gas and reaches the detector at
different periods. Detector detects each component when it reaches the detector.
Common detectors are
(a) Flame Ionization Detector
Ans: Effluents from the column are directed to a hydrogen flame. When pyrolyzed
the organic compounds produce ions and electrons. Detector collects these charge
carriers and produces a current proportional to the amount of ions.
(b) Thermal Conductivity Detector
Ans: The electrical resistance of a heated coil included in a bridge circuit changes as
the effluent gases reach the filament. The resistance change depends on the
thermal conductivity of the gases. The detector is non destructive in nature and the
elutes can be collected.
(c) Electron Capture Detector
Widely used for environmental samples as it responds to halogenated compounds
such as pesticides and PCBs. A radioactive β-emitter like Nickel-63 causes ionization
of carrier gas produces a constant current. When the halogen containing compound
reaches the detector, the halogen atoms capture electrons and the current
markedly reduces. This makes it possible to detect the analytes.
Oven can be programmed to retain the injection port, column and detector at different
temperatures suitable for the separation.

Block diagram of GC

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

2. Consider the following set of replicate measurements.

Total Dissolved
Solids (g/L)
231.5
236.1
232.1
233.3
229.5

For the above set calculate the (a) mean; (b) median; (c) spread; (d) standard deviation
and (e) Coefficient of variation? (Write formulae and show the steps of calculation)

Mean

Standard deviation =

Variance = S2

s
RSD =
x
s
Coefficient of Variation = x X 100

232.5 Mean
232.1 Median
2.437212 Stdev
5.94 Var
0.010452 RSD
1.04% Coefficient
Of Variation

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

3. Calculate the potential of the following electrochemical cells at 25°C ( SEE APPENDIX (P-
13) FOR STANDARD ELECTRODE POTENTIALS):
a) Zn|Zn2+ (0.0955M)|| Co2+(6.78x10-3M)|Co

Ans:
2.303 RT [Zn]
E Zn=¿ E ° ¿ – log
Zn
nF ¿¿

2.303 X 8.314 X 298 [1]

= -0.763V - log
2 X 96485 [0.0955]

= -0.7932V

2.303 RT [Co]
ECo=¿ E ° ¿ – log
Co
nF ¿¿

2.303 X 8.314 X 298 [1]

= -0.277V - log
2 X 96485 [6.78 X 10−7 ]

= -0.3411 V

ECell = ERed - EOx

= 0.4521 V

b) Ag|Ag+(0.1544M)||H+(0.0794M)|O2(1.12atm)Pt
Ans:
2.303 RT [ Ag ]
E Ag=¿ E ° ¿ – log
Ag
nF ¿¿

2.303 X 8.314 X 298 [1]

= 0.799V - log
1 X 96485 [0.1544]

= 0.7510V

2.303 RT [ H 2 O]
EO 2 / Pt=¿ E ° ¿ – log 4
O 2/ pt
nF [O 2 ] [ H 2 ]

2.303 X 8.314 X 298 [1]

= 1.229V - log
4 X 96485 [1.12 X 0. 0 794 4 ]

= 1.164V

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

ECell = ERed-EOx

= 0.413 V

4. A solution containing the complex formed between Bi (III) and thiourea has a molar
absorptivity of 9.32 x103 L cm-1 mol-1 at 470 nm.
a) What is the absorbance of a 6.24x10 -5M solution of the complex at 470nm in a 1.00
cell?
A =abc
= 9.32 x 103 x1 X 6.24x10-5 M
= 0.582
b) What is the molar concentration of the complex in a solution that has the
absorbance described in (a) when measured at 470nm in a 5.00-cm cell?

A = 0.582, b=5cm, a=9.32 x103 L cm-1 mol-1

A
C = = 0.582/9.32 x 103 x 5
ab

= 1.25 x10-5M

5. The distribution constant for X-between n-hexane and water is 9.6. Calculate the
concentration of X remaining in the aqueous layer after 50ml of 0.150M X are treated by
extraction with the following quantities of n-hexane:
(a) One 40.0ml , portion
(b) Two 20.0ml, portions
(c) Four 10.0ml, portions
(d) Eight 5.0ml ,portions

[ ]
i
V aq
Ans: [A]i = [A]0 , where [A]0 and [A]i are the concentrations of
V Org K +V aq
the component ’X’ in Vaq volume of aqueous layer in the beginning and remaining
after ‘i’ number of extraction with’ V org ‘ volume of organic liquid and K the
distribution of coefficient.

Use formula given above. K=9.6, Vaq=50, [A]0=0.150M

(e) One 40.0ml , portion Hint: Vo=40, i=1, Calculate [A]I . Ans:0.017281M
(f) Two 20.0ml, portions Hint: Vo=20, i=2, Calculate [A]I . Ans:0.006403M
(g) Four 10.0ml, portions Hint: Vo=10, i=4, Calculate [A]I . Ans:0.002063M

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

(h) Eight 5.0ml ,portions Hint: Vo=5, i=8, Calculate [A]I . Ans:0.0006891M

PART - B
(Each question carries 1 mark)

1. What is gradient and isocratic elution?

Ans: Elution done with the constant composition of mobile phase is isocratic elution
while the elution done with change in composition of mobile phase is gradient elution.

2. Explain the working of ECD?

Ans: Widely used for environmental samples as it responds to halogenated compounds

such as pesticides and PCBs. A radioactive β-emitter like Nickel-63 causes ionization of
carrier gas produces a constant current. When the halogen containing compound
reaches the detector, the halogen atoms capture electrons and the current markedly
reduces. This makes it possible to detect the analytes.
3. What is DTGS? Where is it used?

Ans: Deuteriated Tri Glycine Sulphate. It is used as a detector in FT-TR.

4. Explain Resonance transition and resonance spectral lines?

Ans: A transition from and to the ground state is called resonance transition and the
corresponding spectral line is called the resonance spectral line

5. What are the different types of atomizers and give examples?

Ans: Continuous and discrete are the two types. For continuous type examples are
plasma and flame atomizers and for the discrete type example is electrothermal
atomizer

6. Explain the production of plasma with a neat diagram?

Ans: Plasma is a conducting gaseous mixture containing large amount of cations and
electrons. Ionization of a gas like argon can produce plasma and the same is done by
either by a dc electrical source, radio-frequency or microwave-frequency sources .
Inductively-Coupled or radio-frequency plasma is produced as follows. The set up
requires 3 concentric quartz tubes. The largest tube has a dia of 2.5cm and the argon

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

gas is made to flow through it when a water cooled induction coil powered by RF
produces a power of 2kW of energy at 27 MHz or 40MHz. A spark from the Tesla coil
initiates ionization by a spark. The ions generated are made to interact with the
fluctuating magnetic field of the induction coil. It makes the ions and electrons to flow in
a closed annular path resulting ohmic heating. The temperature will be quite high and
therefore the quartz tube has to be isolated. This is done by flowing Argon tangentially
around the walls of the tube.

Magnetic field

7. Explain the steps in Electrothermal atomization?

Ans: Drying ,ashing , and atomization

8. What are the different types of background corrections used in AAS?

Ans: Deuterium lamp correction, Smith-Hieftje correction and Zeeman Correction

9. A typical simple infra-red spectrophotometer covers a wavelength range of 3 to 15 µm.

Express its range a) in wavenumbers and b) in hertz
1 1 1
Ans: ν = = m-1=3.33 X105 m-1 , m-1 =6.66 X104 m-1
λ 3 X 10−6 15 X 10−6

c 3 X 108 14 3 X 108 14 13
ν = = −6 =10 Hz , −6 =10 Hz =2 X 10 Hz
λ 3.0 X 10 15.0 X 10

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

10. Explain how the Smith- Hieftje background Correction is applied?

Ans: Hollow cathode lamp is made to pulse at low current for 10ms and high
currents for 0.3ms . The low current pulse estimates both analyte and background
absorbance while high current gives background alone. The difference produces
the true analyte absorbance

11. Give the relation between plate height, plate count and length of a chromatographic
column?
Ans: H = L/N, where H is the thickness of the plate, L is the length of the column and N is
the number of plates.

12. Explain the terms Analyte, sample matrix and blank?

Ans: Analyte is the chemical species of interest, matrix is the various components
present in a sample other than the analyte, a blank contains all the reagents and
solvents except the analyte.
13. Differentiate between precision and accuracy?
Ans: Precision is the reproducibility of the measurements and accuracy is the closeness
of the results to the true value
14. Calculate the potential of the following two half-cells at 25°C that are connected by a
salt bridge: a galvanic cell consisting of a zinc electrode on the left in contact with
0.1364M Zn2+ and a lead electrode on the right immersed in 0.0848M Pb 2+ ( SEE (P-13)
FOR STANDARD ELECTRODE POTENTIALS
Ans:
2.303 RT [Zn]
E Zn=¿ E ° ¿ – log
Zn
nF ¿¿

2.303 X 8.314 X 298 [1]

= -0.763V - log
2 X 96485 [0.1364]

= -0.7886V

2.303 RT [ Pb]
E Pb=¿ E ° ¿ – log
Pb
nF ¿¿

2.303 X 8.314 X 298 [1]

= -0.126V - log
2 X 96485 [0.0848]

= -0.1577 V

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

ECell = ERed-ELeft

= 0.6308 V

15. What is sputtering in a Hollow cathode lamp?

Ans: Metal atoms vaporize from the hollow cathode when accelerated argon ions hit on
it to produce an atomic cloud. This is called sputtering.

PART - C
(Each question carries ½ mark)

1. Which are the detectors used in an Infra-red spectrophotometer?

Ans: Thermocouple, Golay, Bolometer and DTGS

2. What happens to a molecule when it absorbs infra-red light?

Ans:Vibrational energy increases

3. What is meant by atomization?

Ans: A sample is volatilized and decomposed to produce gas phase atoms or ions by this
process.

4. Which are the different statistical parameters generally used to measure precision and
accuracy of experimental data?
Ans: Mean, Standard deviation, Variance, Coefficient of variation.

5. Write down the number of significant figures in each of the following data?
(a) 0.00306 (b) 48000
Ans: a) 3 b) 2

6. How is change in free energy related to electrochemical cell potential? Explain the terms
in the formula?
Ans: △G = -nFEcell , △G, is the change in free energy, n is the number of electrons
involved in the cell reaction, F is Faraday’s constant, E cell is the EMF of the cell.

7. Write the Nernst equation for cell EMF and explain the terms used?

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

2.303 RT
Ans: Ecell =¿E ° ¿ – log K, where K =[c]c [D]d / [A]a [B]b , Ecell is cell EMF, E ° Cell
Cell
nF
is the cell EMF under standard conditions, R is the gas constant, T is the temperature in
absolute scale, n is the number of electrons involved in cell reactions, F is Faraday’s
constant, K is the reaction coefficient.
8. Name the electrode which has zero potential by convention under standard conditions?
Ans: Standard Hydrogen Electrode

9. Give any two examples for electrochemical techniques?

Ans: Potentiometry, Coulometry or Voltammetry

10. Explain macro, semi-micro and micro analysis?

Ans: The classification is based on sample size, Macro (>0.1g), Semi micro (0.01 to
0.1g), Micro (0.0001 to 0.01g)

11. Name the three types of errors occurring in experimental data?

Ans: Systematic error, Random error, Gross error

12. What type of an indicator is ferroin?

Ans: Redox indicator

13. Name the two electrodes used in any Potentiometric measurement?

Ans: Reference electrode and Indicator electrode

14. What is the basic difference between the atomic and molecular spectrum?
Ans: Atomic spectrum is line spectrum and Molecular spectrum is band spectrum.

15. What is the function of a monochromator in a spectrophotometer?

Ans: Isolation of wave length

16. What is the material used to make a sample cell in a UV-VIS spectrophotometer?
Ans: Quartz

17. What is Bremsstrahlung radiation?

Ans: Continuum radiation produced when charged particles are slowed or stopped. In
Plasma

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CHET-307 ANALYTICAL CHEMISTRY
FINAL THEORY EXAMINATION – FIRST SEMESTER (2011-2012 G)

18. What is the fundamental principle behind solvent extraction?

Ans: Distribution law

19. What are the two basic types of Chromatography?

Ans: Planar and Column chromatography

20. Explain the terms elution, eluent and elute?

Ans: Elution is the process of sending the mobile phase through or over the stationary
phase, Eluent is the mobile phase and elute is the components that got separated by
elution.

APPENDIX

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