BINDURA UNIVERSITY OF SCIENCE EDUCATION

DEPARTMENT OF CHEMISTRY
Nkwanele Bhebe
B1441641
2.1
CH204: Analytical Chemistry II
Assignment One
1. Give reasons why split injections are required in GC.
Solution:
a.Spliting reduces the size of the amount of the sample compatible with the
sample capacity of the capillary column.
b. Fast evaporation occur leading to short residence time in the liner
resulting in a small injection plug.
c.The sample vapor mixture flow is of higher velocity.
2. Describe the principles and applications of the thermal conductivity
detector, flame ionization detector and electron capture detector used in
GC.
a) TCD(thermal conductivity detector.)
It is an example of a universal detector. It measures the thermal
conductivity of the analyte and compare it with the thermal
conductivity of the carrier gas. The detector operates on the basis of
the Whitestone bridge. Its minimum detection quantity is 10 -9g/
10pmm with a temperature limit of 4000C.the detector use He as the
carrier gas.

b) Flame ionization detector.

Ions produced since they are charged they cause small electric
currents which can be amplified into a signal.
FID has an operational temperature range which is above 125 0C, this
is to prevent condensation of water.
The detector response is directly proportional to the carbon content of
the organic compound.
Has a minimum detection quantity of 10-11g, temperature limit of
4000C.It uses He/N2 as carrier gases.

c) Electron capture detector.

It is an example of selective detector which responds to samples
containing highly electronegative ions like the Halides.
The carrier gas collides with radioactive -particles from a radioactive
source like Ni causes the generation of more electrons, which
increase the current, when collected by the positive electrode. When
the electronegative analyte enters the detector, the analyte captures
some electrons resulting in the decrease in the standing current
A + eAThe carrier gas used is ultrapure nitrogen, it is fairly stable and has
temperature range of 4000C.MDQ=10-12g

3. What is temperature programming in GC? How does it gain advantage

over single temperature separation?
Temperature programing is a GC sample injection system that
resembles the split/split less injector in structure
The temperature of the injector can be changed in a controllable way
at pre-determined time.
Advantage-it shortens retention time and analytical time hence
reduce peak broardening.

Graph B above shows temperature programming in GC,

temperature is gradually increased at a particular rate during running of a
chromatogram.

4. Explain the instrumentation used UV-VIS with the aid of a block diagram
Light source-------wavelenght selector---------sample-----detector---signal
processor.

.
Components of a spectroscopic unit
Light sources
Light sources emit light of a specific wavelength range

 Hence used light sources depend on the spectroscopic technique and

wavelength.
Wavelength selection
Light produced from the above mentioned sources is polychromatic.
For one to be able to record a spectrum monochromatic light is
required at every stage.
Filters:
These are wavelength selectors that isolate wavelength by either
absorption, or interference
Interference filters are generally more expensive than absorption
filters but have a narrow effective band-width
Filters do not allow for continuous wavelength selection
DETECTORS
Detectors use sensitive transducers. These are devices that convert
chemical or physical property such as pH, conductivity or photon intensity,
to an easily measured electrical signal such as voltage or current. There
are basically two types of transducers: Photo transducers, thermal
transducers

5. Describe the difference between the single beam and double beam
spectrophotometer
Answer
-Single beam has one light path that passes through the sample.
-Reference used is placed alternately with the sample.
-wavelength used is adjusted alternately
-records radiation not absorbed by sample
-has a selection filter that restricts radiation.

Double beam has two light paths, one for the sample and one blank.
-reference and sample are placed at the same time.
Rather complex instrument is used
-automatically vary the wavelength
-records the absorbance as a function of wavelength
-No selection filter.
6. Describe the limitations of Beer Lamberts law.
Answer
Work with dilute concentrations which are less than 0,01M
-Non-monochromatic radiation deviations
7. What is the purpose of GC derivatization?.Name the common
derivatization reaction.
Answer
Derivatization is the replacement of active hydrogen atoms from the analyte
since this are polar and not stable. Normal such hydrogens are from
functional groups like COOH,-SH,-NH.
The purpose of derivatisation is to cause sample volatility and thermal
stability.
Silylation is the common derivatization reaction e.g BSA( N,OBis(trimethylsilyl)acetamide

8. The van Demeter equation relates the column efficiency (measured as H) to

the mobile phase flow rate (u):

a) Sketch a typical van Deemter plot that shows how H depends on u. Clearly
label you.

b) There are three terms in the van Deemter equation: the A term, the B term, and
the C term, each describing a different type of contribution to the band
broadening. Explain the type of band broadening described by 2 of the 3 terms.

There are three terms in the van Deemter equation

Answer
A=Eddy-diffusion parameter, relating to channeling through a nonideal packing
B= diffusion coefficient of the eluting particles in the longitudinal
direction resulting in the dispersion [m2s-1]
C= resistance to mass transfer coefficient to the analyte between the
mobile and stationary phase [s]