ANALYTICAL CHEMISTRY IV

SPECTROSCOPY AND CHROMATOGRAPHY METHODS

Lecturer: Dr. Nita Kusumawati, M.Sc.

Name : Era Melania

Class : PKU 2018
Reg. Number : 18030194085

CHEMISTRY DEPARTMENT
FACULTY OF MATHEMATICS AND NATURAL SCIENCES
SURABAYA STATE UNIVERSITY
2020
Question
1. A sample solution is in the 1 cm cell, after measurement with a
spectrophotometer, it transmits 80% of light at a certain λ. If the absorbance
of the substance at this λ = 2. Calculate the concentration of the substance!
2. A solution containing 1 mg/100 mL of iron (as a complex of iron-thiocyanate)
was observed that transmits 70% of incoming rays.
a. How much the absorbance of the solution at λ?
b. How much fraction of light will be transmitted if the concentration of
the iron solution is enlarged for 4 times?
3. Potassium dichromate and potassium permanganate in 1M of H2SO4 have
overlapping A spectra. K2Cr2O7 has Amax at 440 nm and KMnO4 at 545 nm
(A is actually at 525 nm, but a higher λ is usually used for determination
because of the minimal interference). A mixture of the two substances is
analyzed with measuring the absorbance of solution at the two λ with the
result: A440 = 0,405 dan A545 = 0,712. The cell thickness used is 1 cm.
absorbance of pure solution of K2Cr2O7 1 x 10-3 M and KMnO4 2 x 10-4 M
in 1M H2SO4 using the same cell is:
ACr, 440 = 0,374 ACr, 545 = 0,009
AMn, 440 = 0,019 AMn, 545 = 0,475
Calculate the concentration of bichromate and permanganate in the mixture
solution!
4. A weak acid solution HB (Ka = 1 x 10-3) adsorb UV radiation at λmax = 280
nm with the value of  = 975. Whereas the B- species do not absorb radiation.
If that cell used for measurement of A has a thickness of 1 cm and the
concentration of the acid is 2 x 10-3 M
a. Calculate the A of solution at λmax!
b. If the solution is diluted twice, how is the A?
c. Predict the solution is following the Lambert-Beer's law or not?
5. If a spectrophotometry analysis is done with a sample that has the following
molecule structure:
 a. What analysis methods that can be used and give the reason!
b. Based on the references, the compound has λmax at 510 nm. But,
according to the measurement, the compound shows the maximum
absorption at 525 nm. Analyze what happened, mention the causes,
and how is the solution?
6. If a compound of A has a molecular structure like in the picture below,
absorbs electromagnetic radiation, then:
a. How many electronic transition can occur? Mention!
b. Can this compound analyzed with spectrophotometry UV? Explain!
Answer
1. Known:
 b = 1 cm
 a=2
 T = 80% = 0,8
Asked:
c = ....?
Answer:
 A = - log T = - log 0,8 = - ( -0,0969) = 0,0969
 A = abc

c =

c =

c =

c = 0,04845 g/L

2. Known:
 c= = = 0,01 g/L

 T = 70% = 0,7
Asked:
a. A = ....?
b. P (if the concentration is enlarged 4 times) = ....?
Answer:
a. A = - log T = - log 0,7 = - (-0,1549) = 0,1549
b. A = abc
Because the absorptivity and the cell thickness is same, then:

ab = 

A1 = initial absorbance
c1 = initial concentration
 A2 = final absorbance
c2 = final concentration

A2 =

A2 = 0,6196

A2 = - log T2
T2 = 10-A
T2 = 10-0,6196
T2 = 0,240

log = log

P = 0,240 x 100%
P = 24%

3. Known:
 λ K2CrO4 = 440 nm
 λ KMnO4 = 545 nm
 A440 = 0,405
 A545 = 0,712
 C K2Cr2O7 = 10-3 M
 C KMnO4 = 2 x 10-4 M
 ACr, 440 = 0,374
 ACr, 545 = 0,009
 AMn, 440 = 0,019
 AMn, 545 = 0,475

ACr, 440 = bc

0,374 =  (1) (10-3)
 = 374
AMn, 440 = bc
0,019 =  (1) (2 x 10-4)
 = 95
ACr, 545 = bc
0,009 =  (1) (10-3)
=9
AMn, 545 = bc
0,475 =  (1) (2 x 10-4)
 = 2375

Suppose:
c K2Cr2O7 = x
c KMnO4 = y
A440 = ( Cr, 440) (b) (x) + ( Mn, 440) (b) (y)
0,405 = (374) (1) (x) + (95) (1) (y)
0,405 = 374x + 95y .......(1)

A545 = ( Cr, 545) (b) (x) + ( Mn, 545) (b) (y)

0,712 = (9) (1) (x) + (2375) (1) (y)
0,712 = 9x + 2375y .......(2)
 [0,405 = 374x + 95y] x 2375
[0,712 = 9x + 2375y] x 95

961,875 = 888250x + 225625y

67,64 = 855x + 225625y -
894,235 = 887395x
x = 0,001
0,712 = 9x + 2375y
0,712 = 9(0,001) + 2375y
0,712 = 0,009 + 2375y
2375y = 0,712 - 0,009
2375y = 0,703
y = 0,703 : 2375
y = 0,00029

The concentration of bichromate = 0,001 M

The concentration of permanganate = 0,00029 M

4. Known:
 λmax = 280 nm
 Ka = 10-3
  = 975
 b = 1 cm
 c = 2 x 10-3 M
Asked:
a. A at λmax
b. The value of A if the solution is diluted twice
c. Is the solution follows the Lambert-Beer's laws?
Answer:
a. c = √ =√ =√ x 10-3 = 1,4 x 10-3 = 0,0014 M
 A = bc
A = (975) (1) (0,0014)
A = 1,365
b. Diluted twice (the concentration of is smaller)
C= = 0,0007 M

A = bc
A = 975 x 1 x (0,0007)
A = 0,6825
c. If the concentration increases, the absorption also increases
The graph between absorbance vs concentration according to Lambert
Beer's law should always give a linear curve
1,6
1,4 0,0014; 1,365
1,2
Absorbance

1
0,8
0,0007;
0,6 0,6825
0,4
0,2
0
0 0,0005 0,001 0,0015
Concentration

The A vs C graph of solution is linear, so we can conclude that this

solution is following to Lambert-Beer's law.
5.

a. Based on the bonding structure of the compound above:

 There are double bonding ( orbital), so it is possible that there is
an eletronic transition  → *
 There are non-bonding orbital (n), so it is possible that there is an
electronic transition n → * and n → σ*
 From the possible electronic transition, we can conclude that the
compound can be analyzed with spectrophotometry UV-Vis method
b. The wavelength (λ) shift from 510 nm to 525 nm (higher). It can be
happened cause:
 Auxochrome substitution
When there is an auxochrome substitution, then there is a
change in structure and it can changes the wavelength to the
higher wavelength
 Solvent effect
The concentation of sample is too concentrated can change the
wavelength to the higher.
6.

a. There are 3 types of electronic transitions that can occur:

 n → *
 n → σ*
  → *
b. No. This compound can't be analyzed with spectrophotometry UV
because this compound has 3 types of electronic transition as a
requirement for spectrophotometry UV-Vis analysis method.