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Advanced Lecture4 4444

This lecture discusses the laws of light absorption: 1. Lambert's Law states that absorbance is directly proportional to the thickness of the absorbing medium. Absorbance increases exponentially with thickness. 2. Beer's Law states that absorbance is directly proportional to concentration of the absorbing substance. 3. The Beer-Lambert Law combines these relationships, stating that absorbance is equal to the absorptivity (a constant for a given substance and wavelength) multiplied by the path length and concentration. This law forms the basis of quantitative analysis using spectroscopy. 4. Visual methods like color comparison and balancing depth can be used for qualitative or semi-quantitative analysis but have limitations compared to instrumental methods.

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41 views

Advanced Lecture4 4444

This lecture discusses the laws of light absorption: 1. Lambert's Law states that absorbance is directly proportional to the thickness of the absorbing medium. Absorbance increases exponentially with thickness. 2. Beer's Law states that absorbance is directly proportional to concentration of the absorbing substance. 3. The Beer-Lambert Law combines these relationships, stating that absorbance is equal to the absorptivity (a constant for a given substance and wavelength) multiplied by the path length and concentration. This law forms the basis of quantitative analysis using spectroscopy. 4. Visual methods like color comparison and balancing depth can be used for qualitative or semi-quantitative analysis but have limitations compared to instrumental methods.

Uploaded by

Ziad Hassan
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Advanced Analytical

Techniques

Lecture 4
In Lecture 3
• Spectra-structure correlation
• Types of λmax shifting

• Factors affecting absorption curve


• Laws of Light Absorption
In Lecture 4
• Laws of Light Absorption
• When a beam of light , of intensity I0 , passes through a
transparent cell containing a solution of an absorbing
substance , reduction of the intensity of light may occur
• A portion of the incident light is reflected at the cell faces
,Ir;
• a portion is absorbed by the solution , Ia
• a portion is scattered , Is
• a portion is refracted , In
• and the remainder is transmitted It
• Thus , I0 = Ia + It + Is + Ir + I n + …..
• But for clear solution Is = 0
• And by using a blank consisting of a similar cell filled with the
solvent used , Ir and In will be cancelled.
• Therefore
I0 = I a + I t
• In chemical analysis we are concerned with measuring the
amount of light absorbed , Ia , or transmitted , It , by a solution
and relating this to concentration of some particular ion or
compound in the solution .
• So under experimental condition Io =Ia + Ir by passage of radiation
through the solution It decreases due to absorption by molecules and
Ia increase.
• The decrease in It depends on two parameters,
A- the concentration c of the solution
B- and the thickness of the solution layer through which the light
passes b (light path length).

There two laws which deal with relationship between absorption


and the two variables.
Absorbance & Transmittance Measurement
Io Sample I
Light Wavelength Light
Source Selector Detector
b

We can talk about the fraction of light that was transmitted through
the sample, transmittance (T);

or we can talk about the amount of light that was absorbed by the
sample, absorbance (A). As you can see, one is opposite of the
other:
Relationship Between Absorbance and Transmittance

T = It / Io
%T = (It / Io ) X 100

A = log (Io / I)

So,
A = – log T
A = 2 – log T%
log T% = 2 – A
Fundamental Laws

Lambert's Law: is defined as “the intensity of a beam of


monochromatic radiation decreases exponentially as it passes
through a medium of homogeneous thickness”.
i.e. Absorbance (A) is directly proportional to the thickness
(pathlength) (b) of the solution.

Relationship between Transmitted Light Relationship between


& Pathlength Absorbance and Pathlengh
“Plot of Lambert`s Law "
Mathematically
the above relationship between transmitted light and the thickness
(b) is exponential and A can be expressed as follows:
log (Io / I) = k b
A = k b (Lambert's Law )

In other words, the absorbance of a solution is directly proportional


to pathlength, b , provided that the concentration is constant Thus ,
if we plot absorbance, A ,against pathlength, b, a straight line is
obtained passing through the origin and possessing a slope equal to
k. The latter is a constant for the absorbing substance at a certain
wavelength.
Beer's Law: is defined as “the intensity of a beam of
monochromatic radiation decreases exponentially with the
number of absorbing molecules”.
More simply; the absorbance is proportional to concentration.
(b is constant, at certain λ)

Relationship between Absorbance and


Concentration
“Plot of Beer`s Law "
Mathematically, A = k'c (Beer's law)
where A ; absorbance, c; concentration and k' ; constant at a given λ.
Thus if absorbance , A , is plotted against concentration ,c ,
a straight line is obtained passing through the origin ,o , and
having a slope equal k'.

Beer–Lambert Law:
Beer’s Law: A = k´c where c = concentration
Lambert’s Law: A = k b where b = pathlength
A= k´c and A = k b
Thus , by combining the two laws together
A = a b c (Beer–Lambert law)
A=Єbc
A = A(1%, 1 cm)b c
The Beer–Lambert Law:
A=abc

Where;
a is constant, called absorptivity, which is the
absorbance , when thickness of solution is unity
(i.e., 1 cm) and concentration is unity.

b is the pathlength in cm, and

c is the concentration in grams/Liter.

A absorbance

(Usually, b= 1 cm)
A=εb c
If the unit of concentration is mole/L , (a) is known as molar
absorptivity or epsilon (Є) or molar extinction coefficient.
(unit of Є is L mol-1 cm-1).

A =A (1%, 1 cm) b c
If the unit of concentration is in g%, (a) is known as A (1%, 1 cm).

Relationship Between A(1%, 1cm) and Є :

Є = A(1%, 1cm) x Mwt


10
Both ε and A (1%, 1 cm) are
[1] Characteristic for each absorbing substance.
[2] used for Qualitative purpose.
[3] used for Quantitative analysis.

(If the absorbance of solution containing substance is measured and


we know the value of A(1%, 1 cm) or ε , we can easily calculate the
concentration from Beer–Lambert law.)

A = a b c
[4] A(1%,1cm ) and Є vary with the wavelength and solvent.

Thus if we keep concentration c & pathlength b constant & we use certain


solvent, absorbance A will vary by the variation in wavelength of the
incident light. This variation of A versus λ construct the absorption curve
A- Visual methods:
It may be
a) Standard series method
b) Variable depth or balancing method

a. Standard series method


This method is based on the comparison of the colored sample
with standard series of colors .
Standard colors may be freshly prepared (in series of matched
Nessler tubes)
or a permanent colored system (colored disc or sealed
ampoules are used)
A- Visual methods:
a. Standard series method
A- Visual methods:
a. Standard series method

Standard Sample
solutions

Standard series method for color matching


A- Visual methods:
b. Variable depth or balancing method
The basic principle of this method can be represented as follows:
Nesslerization technique
- Two identical nessler's tubes will be needed ,one for the
standard solution and the other for the test solution.
- Add Equal volume of reagent to develop color in both tubes
- Complete to 50 ml with dist. H2O
- Compare the intensity of the two colors in
both tubes by eye in the light
A- Visual methods:
b. Variable depth or balancing method
We have two cases:
1- If the two colors are of the same intensity
So
Cst = Cunk

2- If the intensity is different,


you will pipette with a graduated
pipette from the darker solution 2ml
by 2 ml and collect them in a cylinder
till the two intensities become the
same.
(for example we will say that the
volume removed was from the
standard solution and it was 10 ml).
A- Visual methods:
b. Variable depth or balancing method
When the two intensities become the same we can say that:
Ast = Aunk
a bstCst = a bunk Cunk
- The absorbitivity (a) is the same as it’s the same
compound developed.
- Cst is known
bst = (50-10) = 40 ml (remaining volume)
bunk = 50 ml
bst (40)
Ct = Cst* in ppm = mg/L
bt (50)
A- Visual methods:
• Disadvantages of visual methods:
1- The eye sensitivity varies with the wavelength.
2- The eye sensitivity varies from one person to another .
3- The eye sensitivity is weakened by prolonged observation and
comparison of colors.
4- Visual methods are used for colored systems only , it is called
colorimetry.

• Advantages of visual methods:


Cheaper and easier than instrumental methods.
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