This article is about measurement of color.

For use in chemistry, see Colorimetry (chemical

method).
Not to be confused with Calorimetry.

Colorimetry (British English: colourimetry) is "the science and technology used to quantify
and describe physically the human color perception."[1] 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 1931 XYZ color space tristimulus values and related quantities.[2]

Contents
[hide]

 1 Instruments
o 1.1 Tristimulus colorimeter
o 1.2 Spectroradiometer, Spectrophotometer, Spectrocolorimeter
o 1.3 Color temperature meter
 2 See also
 3 References
 4 Further reading
 5 External links

[edit] Instruments
Colorimetric equipment is similar to that used in spectrophotometry. Some related equipment is
also mentioned for completeness.

 A tristimulus colorimeter measures the tristimulus values of a color.[3]

 A spectroradiometer measures the absolute spectral radiance (intensity) or irradiance of a
light source.[4]
 A spectrophotometer measures the spectral reflectance, transmittance, or relative
irradiance of a color sample.[4][5]
 A spectrocolorimeter is a spectrophotometer that can calculate tristimulus values.
 A densitometer measures the degree of light passing through or reflected by a subject.[3]
 A color temperature meter measures the color temperature of an incident illuminant.
Two spectral reflectance curves. The object in question reflects light with shorter wavelengths
while absorbing those in others, lending it a blue appearance.

[edit] Tristimulus colorimeter

Main article: Tristimulus colorimeter

In digital imaging, colorimeters are tristimulus devices used for color calibration. Accurate color
profiles ensure consistency throughout the imaging workflow, from acquisition to output.

[edit] 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 400-700 nm 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 characteristics.
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).[5] 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
curve—until they age.[6] On the other hand, tristimulus colorimeters are purpose-built, cheaper,
and easier to use.[7]

The CIE recommends using measurement intervals under 5 nm, even for smooth spectra.[4]
Sparser measurements fail to accurately characterize spiky emission spectra, such as that of the
red phosphor of a CRT display, depicted aside.

[edit] Color temperature meter

Photographers and cinematographers use information provided by these meters to decide what
color balancing should be done to make different light sources appear to have the same color
temperature. If the user enters the reference color temperature, the meter can calculate the mired
difference between the measurement and the reference, enabling the user to choose a corrective
color gel or photographic filter with the closest mired factor.[8]

The normals are lines of equal correlated color temperature.

Internally the meter is typically a silicon photodiode tristimulus colorimeter.[8] The correlated
color temperature can be calculated from the tristimulus values by first calculating the
chromaticity co-ordinates in the CIE 1960 color space, then finding the closest point on the
Planckian locus.

[edit] See also

 Photometry
 Radiometry

[edit] References
 1. ^ Ohno, Yoshi (16 October 2000). "CIE Fundamentals for Color Measurements". IS&T
NIP16 Intl. Conf. on Digital Printing Technologies. pp. 540–45.
http://physics.nist.gov/Divisions/Div844/facilities/photo/Publications/OhnoNIP16-
2000.pdf. Retrieved 2009-06-18.
2. ^ Gaurav Sharma (2002). Digital Color Imaging Handbook. CRC Press. pp. 15–17.
ISBN 9780849309007.
http://books.google.com/?id=OxlBqY67rl0C&pg=PA17&dq=colorimetry+cie+xyz+tristi
mulus+values.
3. ^ a b ICC White Paper #5
4. ^ a b c Lee, Hsien-Che (2005). "15.1: Spectral Measurements". Introduction to Color
Imaging Science. Cambridge University Press. pp. 369–374. ISBN 052184388X.
http://books.google.com/books?id=CzAbJrLin_AC&pg=PA369&dq=spectroradiometer+
spectral&ei=xrewR_GKHZHCzASjo_DRAw&sig=ar9VSAEe55o94rK1FYs04fONBQA
. "The process recommended by the CIE for computing the tristimulus values is to use 1
nm interval or 5 nm interval if the spectral function is smooth"
5. ^ a b Schanda, János (2007). "Tristimulus Color Measurement of Self-Luminous
Sources". Colorimetry: Understanding the CIE System. Wiley Interscience.
doi:10.1002/9780470175637.ch6. ISBN 978-0-470-04904-4.
6. ^ Andreas Brant, GretagMacbeth Corporate Support (2005-01-07). "Colorimeter vs.
Spectro". Colorsync-users Digest. http://lists.apple.com/archives/Colorsync-
users/2005/Jan/msg00118.html. Retrieved 2008-05-06.
7. ^ Raymond Cheydleur, X-Rite (2005-01-08). "Colorimeter vs. Spectro". Colorsync-users
Digest. http://lists.apple.com/archives/Colorsync-users/2005/Jan/msg00120.html.
Retrieved 2008-05-06.
8. ^ a b Salvaggio, Carl (2007). Michael R. Peres. ed. The Focal Encyclopedia of
Photography: Digital Imaging, Theory and Application (4E ed.). Focal Press. p. 741.
ISBN 0240807405. http://books.google.com/?id=VYyldcYfq3MC&pg=RA1-
PA741&lpg=RA1-PA741&dq=three+silicon+photodiodes+%22color+temperature%22.

[edit] Further reading

 Schanda, János D. (1997). "Colorimetry". In Casimer DeCusatis. Handbook of Applied
Photometry. OSA/AIP. pp. 327–412. ISBN 978-1563964169.
http://www.knt.vein.hu/Tantargyak/Szinmeres/Colour.pdf.
 Bala, Raja (2003). "Device Characterization". In Gaurav Sharma. Digital Color Imaging
Handbook. CRC Press. ISBN 9780849309007.
http://chester.xerox.com/~raja/papers/CRC_Chapter5.pdf.
 Gardner, James L. (May–June 2007). "Comparison of Calibration Methods for
Tristimulus Colorimeters" (PDF). Journal of Research of the National Institute of
Standards and Technology 112 (3): 129–138.
http://nvl.nist.gov/pub/nistpubs/jres/112/3/V112.N03.A01.pdf.

[edit] External links

  MacEvoy, Bruce (2008-05-08). "Overview of the development and applications of
colorimetry". Handprint.com.
http://www.handprint.com/HP/WCL/color6.html#colorimetry. Retrieved 2008-07-17.
 Colorimetric equipment by X-Rite Optronik An informative brochure with background
information and specifications of their equipment.

 Konica Minolta Sensing - Precise Color Communication A brief yet informative

introduction to color theory and color measurement, with the emphasis on
communicating color information numerically to avoid subjective interpretations.

 Hunter LAB - A guide to color and appearance A comprehensive guide to measuring

color and appearance of objects. The section provides information on numerical scales
and indices that are used throughout the world to remove subjective measurements and
assumptions. TS

an electromechanical technique of analyzing solutions that measures the current flowing between two
electrodes in the solution as well as the gradually increasing applied voltage to determine respectively
the concentration of a solute and its nature

Polarography
From Wikipedia, the free encyclopedia

Jump to: navigation, search

Polarography is a subclass of voltammetry where the working electrode is a dropping mercury

electrode (DME) or a static mercury drop electrode (SMDE)., useful for its wide cathodic range
and renewable surface. It was invented by Jaroslav Heyrovský.[1][2][3][4][5][6]

Contents
[hide]

 1 Theory of Operation
 2 Limitations
 3 Improvements
 4 Qualitative Information
 5 See also
 6 References
[edit] Theory of Operation

Heyrovský's Polarograph

Polarography is an voltammetric measurement whose response is determined by combined

diffusion/convection mass transport. Polarography is a specific type of measurement that falls
into the general category of linear-sweep voltammetry where the electrode potential is altered in
a linear fashion from the initial potential to the final potential. As a linear sweep method
controlled by convection/diffusion mass transport, the current vs. potential response of a
polarographic experiment has the typical sigmoidal shape. What makes polarography different
from other linear sweep voltammetry measurements is that polarography makes use of the
dropping mercury electrode (DME) or the static mercury dropping electrode.

A plot of the current vs. potential in a polarography experiment shows the current oscillations
corresponding to the drops of Hg falling from the capillary. If one connected the maximum
current of each drop, a sigmoidal shape would result. The limiting current (the plateau on the
sigmoid), called the diffusion current because diffusion is the principal contribution to the flux of
electroactive material at this point of the Hg drop life,.

[edit] Limitations
Heyrovský's Polarograph and DME

There are various limitations in particular for the classical polarography experiment for
quantitative analytical measurements. Because the current is continuously measured during the
growth of the Hg drop, there is a substantial contribution from capacitive current. As the Hg
flows from the capillary end, there is initially a large increase in the surface area. As a
consequence, the initial current is dominated by capacitive effects as charging of the rapidly
increasing interface occurs. Toward the end of the drop life, there is little change in the surface
area which diminishes the contribution of capacitance changes to the total current. At the same
time, any redox process which occurs will result in faradaic current that decays approximately as
the square root of time (due to the increasing dimensions of the Nernst diffusion layer). The
exponential decay of the capacitive current is much more rapid than the decay of the faradaic
current; hence, the faradaic current is proportionally larger at the end of the drop life.
Unfortunately, this process is complicated by the continuously changing potential that is applied
to the working electrode (the Hg drop) throughout the experiment. Because the potential is
changing during the drop lifetime (assuming typical experimental parameters of a 2mV/sec scan
rate and a 4 sec drop time, the potential can change by 8 mV from the beginning to the end of the
drop), the charging of the interface (capacitive current) has a continuous contribution to the total
current, even at the end of the drop when the surface area is not rapidly changing. As such, the
typical signal to noise of a polarographic experiment allows detection limits of only
approximately 10−5 or 10−6 M.

[edit] Improvements
Dramatically better discrimination against the capacitive current can be obtained using the tast
and pulse polarographic techniques. These have been developed with introduction of analog and
digital electronic potentiostats. A first major improvement is obtained, if the current is only
measured at the end of each drop lifetime (tast polarography). An even greater enhancement has
been the introduction of differential pulse polarography. Here, the current is measured before the
beginning and before the end of short potential pulses. The latter are superimposed to the linear
potential-time-function of the voltammetric scan. Typical amplitudes of these pulses range
between 10 and 50 mV, whereas pulse duration is 20 to 50 ms. The difference between both
current values is that taken as the analytical signal. This technique results in a 100 to 1000-fold
improvement of the detection limit, because the capacitive component is effectively suppressed.

[edit] Qualitative Information

Qualitative information can also be determined from the half-wave potential of the polarogram
(the current vs. potential plot in a polarographic experiment). The value of the half-wave
potential is related to the standard potential for the redox reaction being studied.

This technique and especially the DPASV one can be used for environmental analysis, and
especially for marine study for characterisation of Organic matter and metals interactions.[7]

[edit] See also

a technique for analysing and studying ions in solution by using an electrolytic cell with a very small
cathode and obtaining a graph ( polarogram ) of the current against the potential to determine the
concentration and nature of the ions. Because the cathode is small, polarization occurs and each type of
anion is discharged at a different potential. The apparatus ( polarograph ) usually employs a dropping-
mercury cathode

Polarography is a subclass of voltammetry where the working electrode is a dropping mercury

electrode (DME) or a static mercury drop electrode (SMDE)., useful for its wide cathodic range
and renewable surface. It was invented by Jaroslav Heyrovský.[1][2][3][4][5][6]

Contents
[hide]

 1 Theory of Operation
  2 Limitations
 3 Improvements
 4 Qualitative Information
 5 See also
 6 References

[edit] Theory of Operation

Heyrovský's Polarograph

Polarography is an voltammetric measurement whose response is determined by combined

diffusion/convection mass transport. Polarography is a specific type of measurement that falls
into the general category of linear-sweep voltammetry where the electrode potential is altered in
a linear fashion from the initial potential to the final potential. As a linear sweep method
controlled by convection/diffusion mass transport, the current vs. potential response of a
polarographic experiment has the typical sigmoidal shape. What makes polarography different
from other linear sweep voltammetry measurements is that polarography makes use of the
dropping mercury electrode (DME) or the static mercury dropping electrode.

A plot of the current vs. potential in a polarography experiment shows the current oscillations
corresponding to the drops of Hg falling from the capillary. If one connected the maximum
current of each drop, a sigmoidal shape would result. The limiting current (the plateau on the
sigmoid), called the diffusion current because diffusion is the principal contribution to the flux of
electroactive material at this point of the Hg drop life,.

[edit] Limitations
Heyrovský's Polarograph and DME

There are various limitations in particular for the classical polarography experiment for
quantitative analytical measurements. Because the current is continuously measured during the
growth of the Hg drop, there is a substantial contribution from capacitive current. As the Hg
flows from the capillary end, there is initially a large increase in the surface area. As a
consequence, the initial current is dominated by capacitive effects as charging of the rapidly
increasing interface occurs. Toward the end of the drop life, there is little change in the surface
area which diminishes the contribution of capacitance changes to the total current. At the same
time, any redox process which occurs will result in faradaic current that decays approximately as
the square root of time (due to the increasing dimensions of the Nernst diffusion layer). The
exponential decay of the capacitive current is much more rapid than the decay of the faradaic
current; hence, the faradaic current is proportionally larger at the end of the drop life.
Unfortunately, this process is complicated by the continuously changing potential that is applied
to the working electrode (the Hg drop) throughout the experiment. Because the potential is
changing during the drop lifetime (assuming typical experimental parameters of a 2mV/sec scan
rate and a 4 sec drop time, the potential can change by 8 mV from the beginning to the end of the
drop), the charging of the interface (capacitive current) has a continuous contribution to the total
current, even at the end of the drop when the surface area is not rapidly changing. As such, the
typical signal to noise of a polarographic experiment allows detection limits of only
approximately 10−5 or 10−6 M.

[edit] Improvements
Dramatically better discrimination against the capacitive current can be obtained using the tast
and pulse polarographic techniques. These have been developed with introduction of analog and
digital electronic potentiostats. A first major improvement is obtained, if the current is only
measured at the end of each drop lifetime (tast polarography). An even greater enhancement has
been the introduction of differential pulse polarography. Here, the current is measured before the
beginning and before the end of short potential pulses. The latter are superimposed to the linear
potential-time-function of the voltammetric scan. Typical amplitudes of these pulses range
between 10 and 50 mV, whereas pulse duration is 20 to 50 ms. The difference between both
current values is that taken as the analytical signal. This technique results in a 100 to 1000-fold
improvement of the detection limit, because the capacitive component is effectively suppressed.

[edit] Qualitative Information

Qualitative information can also be determined from the half-wave potential of the polarogram
(the current vs. potential plot in a polarographic experiment). The value of the half-wave
potential is related to the standard potential for the redox reaction being studied.

This technique and especially the DPASV one can be used for environmental analysis, and
especially for marine study for characterisation of Organic matter and metals interactions.[7]

[edit] See also