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Analytical Chemistry Questions

Analytical Chemistry Questions

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05/15/2013

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WARANGAL
V .  A   D   I   T   Y  A    V  A   R   D   H  A   N   W   W   W .  A   D   I   C   H   E   M  A   D   I .   C  O   M
1
Updated on22nd Nov, 2009and going to be updated frequently. For recent updates, visit
ANALYTICAL CHEMISTRY QUESTIONS AND EXPLANATION44)The unit of molar absorptivity is:1. L mol
–1
cm
–1
2. L
–1
mol cm
–1
3. L mol cm
–1
4. L mol cmExplanation:Beer-Lambert law
A
=

.c.l
WhereA = absorbancec = molar concentration
l
= pathlength (in cm)

= molar extinction coefficient or molar absorptiviy =
A
cl
(note:

is pronounced as epsilon)Hence the units are usually in M
-1
cm
-1
or L mol
-1
cm
-1
( ‘A’ has no units: see below)As 1 liter = 1000 cm
3
, the unit may be sometimes cm
2
mol
-1
, especially in old literature.
Absorbance (A) = log
10
(1/T)= -log
10
T= -log
10
(I /I
o
)WhereT = transmittance = I /I
o
I = intensity of the transmitted lightI
o
= intensity of the initial incident light* Remember transmittance (T) is inversely related to absorbance (A)Other equations to remember:
10
100A = log( )%T
= 2 - log
10
(%T)
BEER-LAMBERT LAW:
The actual absorbance,
A
, of a sample is
dependent
on thepathlength
l
(in cm) and the concentration
c
(molar conc.) of the species.Mathematically:
A = .c.
l

*

is a is a measure of the amount of light absorbed per unit concentration at a givenwavelength.*

is an intrinsic property of the compound;
Limitations:
* Beer-Lambert law is a limiting law. It is only valid for dilute solutions. At higher concentra-tions, the electrostatic interactions between neighbouring molecules distort the energy levelswhich cause deviation from the law.* Deviations also occur when the molecules undergo chemical change in solutions (this mayoccur due to change in concentration or pH).

WARANGAL
V .  A   D   I   T   Y  A    V  A   R   D   H  A   N   W   W   W .  A   D   I   C   H   E   M  A   D   I .   C  O   M
2
eg.,
Yellow
chromate and
orange
dichromate are in equilibrium with each other in aqueoussolution. The equilibrium shifts to the right if p
H
is decreased (when acid is added) and shifts tothe left if p
H
is increased (when base is added).
2-+2-4272
2 CrO(aq) + 2 H (aq) CrO(aq) + HO (l)yellow orange

Hence the absorbance for this solution depends on the p
H
.* There should be no scattering of light.* There should be no fluorescence or phosphorescence
INTERESTING
Guess the molar absorbtivity of Cu
2+
ions in an aqueous solution of CuSO
4
. Whether 20 or100,000 L mol
-1
cm
-1
?You may prefer higher value as the copper sulphate solutions you have seen are usually abeautiful bright blue in colour. However, its molar absorbtivity value is 20 L.mol
-1
.cm
-1
! Thebright blue colour is seen because the concentration of the solution is very high.Now consider the beta-carotene which is responsible for the colour of carrots. It is foundat exceedingly low concentrations and still imparts beautiful orange color as its molarabsorbtivity is 100,000 L.mol
-1
.cm
-1
.
Additional questions:44.1) What is the concentration of a solution whose absorbance is 0.21 when placed in a tubeof path length 10 cm (
max

= 245 nm and
max

= 31,500 M
-1
cm
-1
)
Ans:-
-7
A0.21c= = = 6.67 x 1031500 x 10
M l

44.2) If the visible spectrum of [Ti(OH
2
)
6
]
3+
has an absorbance maximum at 0.9 at 510 nm andthe spectrum was recorded on a 0.20 M solution in a 1.0 cm cell, what would be the valueof
510

?
Ans:-
510

= 4.5 cm
-1
M
-1
44.3) Transferrin is an iron-transport protein found in blood. Desferrioxamine B is an ironchelator used to treat patients suffering from iron overload. Both are colourless in theabsence of iron. The following data was obtained in aqueous solution using a 1.00 cm pathlength cell for both species when fully complexed with iron:----------------------------------------------------------------------------------
max

/ nm
max

/ L mol
–1
cm
–1
iron-transferriniron-desferrioxamine B

WARANGAL
V .  A   D   I   T   Y  A    V  A   R   D   H  A   N   W   W   W .  A   D   I   C   H   E   M  A   D   I .   C  O   M
3
-----------------------------------------------------------------------------------4283540273047041702290-----------------------------------------------------------------------------------Calculate the absorbance at 470 nm of a solution that is 11.0

M in iron-transferrin and69.5

M in iron-desferrioxamine B, assuming both are fully complexed and that the cellpath length is 1.00 cm.
Ans:-

M = 10
-6
MFor iron transferrin, A = 4.6 x 10
-2
For iron-desferrioxamine B, A = 1.6 x 10
-1
= 16 x 10
-2
Total = 4.6 x 10
-2
+ 16 x 10
-2
= 2.06 x 10
-1
44.4) The percentage transmittance of a transition metal complex at 360 nm and at 25
0
C is25% for a 6 x 10
-4
mol L
-1
solution in a 1 cm cell. The molar absorption coefficient in theunit of L mol
-1
cm
-1
is(a)
-3
1.0x10
(b)
3
1.0x10
(c)
3
2.0x10
(d)
4
1.0x10
Ans:-
10
100A = log( )%T
= 2 - log
10
(%T)= 2 - log25= 2 - 2log5= 2 - (2 x 0.6990)
0.6
3-1-1-4
A0.6= = = 1 x 10 L molcm6 x 10x 1
cl

44.5) A solution of a compound shows a transmittance of 0.800 in a 1.0 cm cell at 525 nm.The transmittance in a 5.0 cm cell at the same wavelength would be(a) 0.160(b) 0.654(c) 0.240(d) 0.317
Ans:-
1011210211221011210210102-122
log log log=loglog0.8001or =5log-logT5 x -log0.8 = 5 x -(3log2 + log10) =5 x(-0.9 +1) = 0.5or T=antilog(- 0.5) = antil
A A  A l But  A lll  Hence
og (1.5)0.316
5)A solution containing 5 ppm of KMnO
4
(F.W = 158) has a transmittance of 0.360 mea-sured in a 1cm cell at 500nm. The molar absorptivity of KMnO
4
in L mol
-1
cm
-1
is(a) 1.1 x 10
4
(b) 1.4 x 10
4
(c) 1.9 x 10
4
(d) 2.7 x 10
4