We start with the transmission of light over the distance of ,
and differentiate it with respect to the absorption coefficient:
Now we interpret the differentials
and
as an error
of the calculated absorption coefficient which is the result of the measurement error
of the transmission.
From this, for the absolute absorption coefficient, it follows:
The relative error becomes:
In order to find a possible minimum of the relative error, we differentiate it with respect to the absorption coefficient
,
and equate the derivate with zero. After reducing, the following is obtained:
The measuring distance which shows the smallest error in the calculated absorption coefficient hence is numerically equal to the inverse absorption coefficient:
If inserted in the equation for the transmission, it follows:
The best conditions for precise measurements are given when the intensity of light has declined through absorption to around 37% of the starting value.
Task: Relative and absolute errors of the absorption coefficient ↓ ↑
The optical length of cuvettes in photometry usually is 1 cm. For the analysis of slightly absorbing liquids, cuvettes with a length of 5 or 10 cm can be used as well. The length of 1 m would require a special construction.
We assume that the measurement is - for example due to an imprecise measurement of the light intensity or a low resolution of the measuring device - only possible to be done with an error not better than .
Please calculate for the given path lengths and liquids with assumed absorption coefficients of 0.05 - 0.1 - 0.2 - 1.0 - 2.3 - 5.0 m-1
- the values of the transmission
- the absolute and the relative errors of the absorption coefficients
Work out what the smalles possible relative error for the mentioned cuvettes is, when the condition of
is met and interpret your results.
Solution: Relative and absolute errors of the absorption coefficient ↓ ↑
Be x=1 m |
c /m |
T |
Δc/c |
Δc /m |
|
0.05 |
0.951 |
0.105 |
0.0053 |
|
0.10 |
0.905 |
0.055 |
0.0055 |
|
0.20 |
0.819 |
0.030 |
0.0060 |
|
1.0 |
0.368 |
0.0136 |
0.0136 |
|
2.3 |
0.10 |
0.0217 |
0.050 |
|
5.0 |
6.7·10-3 |
0.1484 |
0.742 |
Be x=1 cm |
c /m |
T |
Δc/c |
Δc /m |
|
0.05 |
0.9995 |
10 |
0.5 |
|
0.10 |
0.9990 |
5 |
0.5 |
|
0.20 |
0.9980 |
2.5 |
0.5 |
|
1.0 |
0.9900 |
0.5 |
0.5 |
|
2.3 |
0.9773 |
0.22 |
0.5 |