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Part I

Last Update: 6 December 2017
M - 165
Colorimetry and Spectrophotometry M

Colorimetry or Colourimetry is "the science and technology used to quantify and describe physically the
human color perception." It is similar to spectrophotometry, but is distinguished by its interest in reducing
spectra to the physical correlates of color perception, most often the CIE XYZ tristimulus values and related
Absorption colorimeter
In physical chemistry, a colorimeter is a device used to test the concentration of a solution by measuring its
absorbance of a specific wavelength of light. To use this device, different solutions must be made, and a
control (usually a mixture of distilled water and another solution) is first filled into a cuvette and placed
inside a colorimeter to calibrate the machine. Only after the device has been calibrated can you use it to find
the densities and/or concentrations of the other solutions. You do this by repeating the calibration, except
with cuvettes filled with the other solutions. The filter on a colorimeter must be set to red if the liquid is
blue. The size of the filter initially chosen for the colorimeter is extremely important, as the wavelength of
light that is transmitted by the colorimeter has to be same as that absorbed by the substance.
Spectroradiometer, Spectrophotometer, Spectrocolorimeter
The absolute spectral power distribution of a light source can be measured with a spectroradiometer, which
works by optically collecting the light, then passing it through a monochromator before reading it in narrow
bands of wavelength.
Reflected color can be measured using a spectrophotometer (also called
spectroreflectometer or reflectometer), which takes measurements in the
visible region (and a little beyond) of a given color sample. If the custom of
taking readings at 10 nanometer increments is followed, the visible light range
of 400-700nm will yield 31 readings. These readings are typically used to draw
the sample's spectral reflectance curve (how much it reflects, as a function of
wavelength); the most accurate data that can be provided regarding its
CRT phosphors
The readings by themselves are typically not as useful as their tristimulus values, which can be converted
into chromaticity co-ordinates and manipulated through color space transformations. For this purpose, a
spectrocolorimeter may be used. A spectrocolorimeter is simply a spectrophotometer that can estimate
tristimulus values by numerical integration (of the color matching functions' inner product with the
illuminant's spectral power distribution). One benefit of spectrocolorimeters over tristimulus colorimeters is
that they do not have optical filters, which are subject to manufacturing variance, and have a fixed spectral
transmittance curveuntil they age. On the other hand, tristimulus colorimeters are purpose-built, cheaper,
and easier to use.
The CIE recommends using measurement intervals under 5 nm, even for smooth spectra. Sparser
measurements fail to accurately characterize spiky emission spectra, such as that of the red phosphor of a
CRT display, depicted aside.

Basic Principles
A spectrophotometer is employed to measure the amount of light that a sample absorbs. The instrument
operates by passing a beam of light through a sample and measuring the intensity of light reaching a
In physics, spectrophotometry is the quantifiable study of electromagnetic spectra. It is more specific than
the general term electromagnetic spectroscopy in that spectrophotometry deals with visible light, near-
ultraviolet, and near-infrared. Also, the term does not cover time-resolved spectroscopic techniques.
Spectrophotometry involves the use of a spectrophotometer. A spectrophotometer is a photometer (a device
for measuring light intensity) that can measure intensity as a function of the color, or more specifically, the
wavelength of light. Important features of spectrophotometers are spectral bandwidth and linear range of
absorption measurement.
Perhaps the most common application of spectrophotometers is the measurement of light absorption, but
they can be designed to measure diffuse or specular reflectance.[clarification needed] Strictly, even the emission
half of a luminescence instrument is a kind of spectrophotometer.
The use of spectrophotometers is not limited to studies in physics. They are also commonly used in other
scientific fields such as chemistry, biochemistry, and molecular biology.[1] They are widely used in many
industries including printing and forensic examination.

There are two major classes of spectrophotometers; single beam and double beam. A double beam
spectrophotometer compares the light intensity between two light paths, one path containing a reference
sample and the other the test sample. A single beam spectrophotometer measures the relative light intensity
of the beam before and after a test sample is inserted. Although comparison measurements from double
beam instruments are easier and more stable, single beam instruments can have a larger dynamic range and
are optically simpler and more compact.
Historically, spectrophotometers use a monochromator containing a diffraction grating to produce the
analytical spectrum. There are also spectrophotometers that use arrays of photosensors. Especially for
infrared spectrophotometers, there are spectrophotometers that use a Fourier transform technique to acquire
the spectral information quicker in a technique called Fourier Transform InfraRed...
The spectrophotometer quantitatively compares the fraction of light that passes through a reference solution
and a test solution. Light from the source lamp is passed through a monochromator, which difracts the light
into a "rainbow" of wavelngths and outputs narrow bandwidths of this diffracted spectrum. Discrete
frequencies are transmitted through the test sample. Then the intensity of the transmitted light is measured
with a photodiode or other light sensor, and the transmittance value for this wavelength is then compared
with the transmission through a reference sample.
In short, the sequence of events in a spectrophotometer is as follows:
1. The light source shines into a monochromator.
2. A particular output wavelength is selected and beamed at the sample.
3. The sample absorbs light.
4. The photodetector behind the sample responds to the light stimulus and outputs an analog electronic
current which is converted to a usable format.

5. The numbers are either plotted straight away, or are fed to a computer to be manipulated (e.g. curve
smoothing, baseline correction and coversion to absorbency, a log function of light transmittance
through the sample)
Many spectrophotometers must be calibrated by a procedure known as "zeroing." The absorbency of a
reference substance is set as a baseline value, so the absorbencies of all other substances are recorded
relative to the initial "zeroed" substance. The spectrophotometer then displays % absorbency (the amount of
light absorbed relative to the initial substance).[1]

UV and IR spectrophotometers
The most common spectrophotometers are used in the UV and visible regions of the spectrum, and some of
these instruments also operate into the near-infrared region as well.
Visible region 400-700 nm spectrophotometry is used extensively in colorimetry science. Ink manufacturers,
printing companies, textiles vendors, and many more, need the data provided through colorimetry. They take
readings in the region of every 10- 20 nanometers along the visible region, and produce a spectral
reflectance curve or a data stream for alternative presentations. These curves can be used to test a new batch
of colorant to check if it makes a match to specifications e.g., iso printing standards.
Traditional visual region spectrophotometers cannot detect if a colorant or the base material has
fluorescence. This can make it difficult to manage color issues if for example one or more of the printing
inks is fluorescent. Where a colorant contains fluorescence, a bi-spectral fluorescent spectrophotometer is
used. There are two major setups for visual spectrum spectrophotometers, d/8 (spherical) and 0/45. The
names are due to the geometry of the light source, observer and interior of the measurement chamber.
Scientists use this machine to measure the amount of compounds in a sample. If the compound is more
concentrated more light will be absorbed by the sample; within small ranges, the Beer-Lambert law holds
and the absorbance between samples vary with concentration linearly. In the case of printing measurements
2 alternative settings are commonly used- without/with uv filter to control better the effect of uv brighteners
within the paper stock.
Samples are usually prepared in cuvettes; depending on the region of interest, they may be constructed of
glass, plastic, or quartz.

IR spectrophotometry
Spectrophotometers designed for the main infrared region are quite different because of the technical
requirements of measurement in that region. One major factor is the type of photosensors that are available
for different spectral regions, but infrared measurement is also challenging because virtually everything
emits IR light as thermal radiation, especially at wavelengths beyond about 5 m.
Another complication is that quite a few materials such as glass and plastic absorb infrared light, making it
incompatible as an optical medium. Ideal optical materials are salts, which do not absorb strongly. Samples
for IR spectrophotometry may be smeared between two discs of potassium bromide or ground with
potassium bromide and pressed into a pellet. Where aqueous solutions are to be measured, insoluble silver
chloride is used to construct the cell.

Spectroradiometers, which operate almost like the visible region spectrophotometers, are designed to
measure the spectral density of illuminants in order to evaluate and categorize lighting for sales by the
manufacturer, or for the customers to confirm the lamp they decided to purchase is within their
specifications. Components:
1. The light source shines onto or through the sample.
2. The sample transmits or reflects light.
3. The detector detects how much light was reflected from or transmitted through the sample.
4. The detector then converts how much light the sample transmitted or reflected into a number.

Experimental Procedure
The following simulation illustrates the procedures for making spectrophotometric measurements.
First, the intensity of light (I0) passing through a blank is measured. The intensity is the number of
photons per second. The blank is a solution that is identical to the sample solution except that the
blank does not contain the solute that absorbs light. This measurement is necessary, because the cell
itself scatters some of the light.
Second, the intensity of light (I) passing through the sample solution is measured. (In practice,
instruments measure the power rather than the intensity of the light. The power is the energy per
second, which is the product of the intensity (photons per second) and the energy per photon.)
Third, the experimental data is used to calculate two quantities: the transmittance (T) and the
absorbance (A).
A = - log10 T

The transmittance is simply the fraction of light in the original beam that passes through the sample and
reaches the detector. The remainder of the light, 1 - T, is the fraction of the light absorbed by the sample.
(Do not confuse the transmittance with the temperature, which often is given the symbol T.)
In most applications, one wishes to relate the amount of light absorbed to the concentration of the absorbing
molecule. It turns out that the absorbance rather than the transmittance is most useful for this purpose. If no
light is absorbed, the absorbance is zero (100% transmittance). Each unit in absorbance corresponds with an
order of magnitude in the fraction of light transmitted. For A = 1, 10% of the light is transmitted (T = 0.10)
and 90% is absorbed by the sample. For A = 2, 1% of the light is transmitted and 99% is absorbed. For A =
3, 0.1% of the light is transmitted and 99.9% is absorbed.
Using the simulation below, perform the following steps:
Measure the intensity of light passing through the blank.
Measure the intensity of light passing through the sample.
Calculate the transmittance.
Calculate the absorbance.
Note: For each measurement, run the simulation long enough to detect at least 1000 photons. There is
substantial random error in the intensity, and the more photons that are counted, the lower the relative
uncertainty in the results.