Philippine Journal of Science

144 (2): 117-127, December 2015

ISSN 0031 - 7683
Date Received: ?? Feb 20??

Determination of Chromium and Manganese

in Steel Using Digital Photometry of Solutions

Jason DR Vedad1, Josefina L. Solivas1, Jose H. Santos2 and

Ernesto J. del Rosario1*

Institute of Chemistry, College of Arts and Sciences

1

University of the Philippines Los Baos, Laguna, Philippines

2
Chemical Sciences Programme, Faculty of Science
Universiti Brunei Darussalam, Bandar Seri Begawan, Brunei Darussalam

The chromium and manganese contents of a steel sample were determined using digital
photometric analysis. Digital still photographs of dichromate and permanganate solutions
were taken using 10-megapixel (MP) and 12-MP digital cameras. RGB values were determined
using the RGB Analysis of Image Colors and SI ColorPicker which are free-access software.
G-B and a*-b* plots were constructed in order to calculate the analyte concentrations, which
were then compared with those obtained by conventional spectrophotometric analysis. The
concentrations obtained with the two digital cameras showed no significant differences
at 95% confidence level from those calculated based on RGB values using the two software.
Use of G-B plots resulted in greater accuracy than a*-b* plots for calculating chromium
and manganese concentrations. Digital photometry (color image processing) was found to be
reproducible and accurate and is a cheaper alternative to conventional spectrophotometry for
determining the chromium and manganese contents of steel.

Key words: chromium determination, digital photometry, manganese determination, steel analysis

INTRODUCTION Chromium determination in rocks and mineral samples

Steel consists mainly of iron and small amounts of
carbon plus alloying metals like manganese, chromium,
vanadium. These added metals make the steel harder and
stronger but reduce ductility. It contains 100 ppm - 10%
chromium and 0.1% - 1% manganese (Ashby and Jones
1992). Colorimetric analysis of chromium and manganese
is used in some standard methods although spectroscopic
methods such as atomic absorption and inductively-
coupled plasma emission spectroscopy, as well as neutron
activation analysis and X-ray fluorometry are more
popular. In some alloys, chromium can be determined by
differential spectrophotometry where other metals like
nickel and manganese have no significant interference.
*Corresponding author: ejdros@yahoo.com
may be done by carbonate-magnesium oxide fusion and
colorimetry with diphenylcarbazide (Fuge 1967). Rapid
determination of chromium is achieved by persulfate
oxidation and spectrophotometric determination with
a flow-through cell where other interfering ions are
separated by ion-exchange chromatography with
perchloric acid as eluent (Fritz and Sickafoose 1972).
Manganese in steel may be determined after extraction
as dimethyldistearylammonium permanganate followed
by spectrophotometric analysis of the dichloromethane
solution (Barakat 1999). Recently, manganese
determination in steel based on the violet color of
permanganate was facilitated using a portable instrument
with light emitting diodes at 525nm as light source
(Mahapatra et al. 2009).

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Philippine Journal of Science
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The concentration of colored solutes is commonly
determined using a visible spectrophotometer. Alternatively,
a digital camera may be used to take photographs of the
solutions and color analysis of the photographs may be
used in order to calculate the concentration of colored
species (after suitable calibration with standard solutions).
This digital photometric method is based on colorimetry
which quantifies the human color perception using the
International Commission for Illumination (CIE) system
(CIE 2004). This system uses a chromaticity diagram, for
the representation of perceived colors. The RGB model
describes the amounts of the primary colors red (R), green
(G), and blue (B) that contribute to the color of the image.
The RGB values may be represented by different notations:
the arithmetic, percentage, digital 8-bit per channel and
digital 26-bit per channel.
Few analytical methods for chemical analysis based on digital
photometry have been developed. One innovation in this
field involves tristimulus colorimetry that uses RGB values
derived from digital photographic data. The RGB values,
after transformation into measures of redness-greenness
and yellowness-blueness, have been applied to the analysis
of iron and residual chlorine in water (Suzuki, et al. 2006).
RGB color analysis has also been applied to blood glucose
determination (Raja and Sankaranarayanan 2007) and soluble
protein concentration (Yanos et al. 2013). The RGB Analysis
of Color Image, which is a Java Applet available from the
Internet, allows the determination of RGB values of a given
area of a digital still photograph. It was initially applied to
the study of insect colors in order to accurately duplicate
them from the generated RGB values (Byers 2006). The SI
ColorPicker, which is also freely downloadable from the
Internet, is a similar computer software that presents RGB
values in decimal format. However, it calculates RGB values
per pixel and not per area of the photograph.
The present study deals with the application of digital
photometry to the simultaneous analysis of chromium
and manganese in steel after converting the metals into
dichromate and permanganate, respectively. A digital
camera was used to take still photographs of the colored
solutions. Color analysis of the digital photographs was
done using two software downloaded from the Internet,
namely RGB Analysis of Color Image and SI ColorPicker.
The results were compared in accuracy and reproducibility
with those using conventional visible spectrophotometry.
MATERIALS AND METHODS
Reagents and chemicals
All chemicals used in the experiments are reagent
grade from Sigma-Aldrich. Filings were prepared from
118
Vedad et al: Cr and Mn contents of steel
determined by digital photometry
commercially available stainless steel and used as sample
for determination of chromium and manganese.
Equipment
A Shimadzu Mini 1240 Spectrophotometer was used for
spectrophotometric measurements. Digital photographic
data were gathered using two digital cameras: 12
megapixel Olympus FE-46 and 10 megapixel Nikon
Coolpix L20. For RGB analysis, a laptop computer with
Windows XP operating system was used after installing
Java applet RGB Analysis of Image Colors and SI
ColorPicker software. The generation of surface equations
was done using the TableCurve 3D version 4.0, also
installed in the same computer.
Sample preparation
One gram of steel sample was weighed and placed in
a 250-mL beaker into which deionized water (50 mL),
concentrated sulfuric acid (10 mL) and concentrated
phosphoric acid (5 mL) were added. The mixture was
heated for at least half an hour at 80-90 degrees C until
effervescence ceased. Concentrated nitric acid (5 mL)
was added after cooling the mixture, which was heated
again until the steel sample completely dissolved. The
resulting solution, after cooling, was transferred into
a 250-mL volumetric flask, diluted to the mark with
deionized water, and then filtered in order to remove any
undissolved impurities. A 25-mL aliquot of the solution
was transferred into an Erlenmeyer flask and 5 mL each
of concentrated solutions of sulfuric acid and phosphoric
acid were added. One mL of 1M silver nitrate solution was
then added followed by 5 g of potassium metapersulfate.
The mixture was swirled and then heated to boiling for five
minutes. The mixture was cooled slightly and potassium
metaperiodate (0.5 g) was added. The mixture was heated
again to gentle boiling for 5 minutes and then diluted to
50 mL with deionized water. Three trials were performed.
Visible spectrophotometric determination
A set of standard solutions of KMnO4 and K2Cr2O7 was
prepared with concentrations in the range of 1.0 - 1010-4 M
(in increments of 1.010-4 M) for permanganate standards
and 4.0 - 4010-4 M (in increments of 4.010-4 M) for
dichromate standards. The standard solutions were
prepared to a final sulfuric acid concentration of 0.5M. A
blank was prepared by making a 1:1 (v/v) solution of 1M
H2SO4 and deionized water. Spectral scans of the 5.010-4
M KMnO4 and 2.010-3 M K2Cr2O7 standard solutions
were done and the wavelengths of maximum absorption
(c) were determined.
The absorbances of the standard solutions were determined
at the corresponding values of max for KMnO4 and
K 2 Cr 2 O 7 . The absorbance of each solution at the
Philippine Journal of Science
Vol. 144 No. 2, December 2015
appropriate max was plotted versus concentration. The
molar absorptivities () at the two wavelengths for both
compounds were determined using the Beer-Lamberts
Law. The absorbances of the steel samples were measured
at the corresponding max and the concentrations of KMnO4
and K2Cr2O7 in these solutions were determined using the
following equations:
1= 1, + 1, (1) potassium dichromate, a solution with final permanganate
4 4 2 2 7 2 2 7
2=2, + 2, (2) 0.001M, respectively, was prepared with final sulfuric
4 4 2 2 7 2 2 7
Digital photometric analysis
Two 15-watt fluorescent bulbs were placed 21.6 cm
away from the sample slot, each at a 45 degree angle.
The digital camera was placed 15.2 cm directly above
the circular sample holder. The latter was made of white
plastic polymer with ten palette wells each containing
0.5 mL of analyte solution. The digital photometric
set-up has been described with a drawing in a previous
publication from the authors laboratory (Yanos et al.
2013). It was placed in a dark room where no other light
source was available. The flash feature of the camera
was deactivated.
Ten KMnO 4 solutions with concentrations of 0.2
2.010-3 M (in increments of 0.210-3M) and ten K2Cr2O7
solutions with concentrations of 0.8 8.010-3 M (in
increments of 0.810-3 M) were prepared. Photographs
of these solutions were taken in the experimental set-up
using the 10 megapixel Nikon Coolpix L20 digital camera.
The RGB values were determined using the software RGB
Analysis of Image Colors.
Standard solutions of KMnO 4 and K 2 Cr 2 O 7 were
prepared with concentrations mentioned above and
1:1 (v/v) mixtures of these standard solutions were
prepared, as well as the blank, with a final H 2SO 4
concentration of 0.5M. The mixed standard solutions
(0.5 mL each) were placed in white palette wells and
digital still photographs were taken with the two digital
cameras using the timer mode. A digital still photograph
of the unknown sample was also taken using the same
set-up and camera settings.
The digital still photographs were analyzed by determining
the RGB values for each standard and sample using the
RGB Analysis of Image Colors (Byers 2006).
Test for repeatability
The digital photometric analysis of the steel sample was
repeated in order to determine its intra-day precision using
the same equipment and doing the duplicate analysis on
the same date by the same analyst. The results of the
second analysis were compared with the earlier results.
Vedad et al: Cr and Mn contents of steel
determined by digital photometry
Validation of accuracy
The accuracy of the photometric method for determining
manganese and chromium was validated by analyzing a
solution containing known concentrations of permanganate
and dichromate using both visible spectrophotometry and
digital photometry.
Using reagent grade potassium permanganate and
and dichromate concentrations of 0.00025M and
acid concentration of 0.5M. The prepared solution was
analyzed using visible spectrophotometry and digital
photometry and three trials were done. Results of both
methods were compared with the theoretical value.
Statistical analyses of results
The concentrations determined using both visible
spectrophotometric and digital photometric methods were
compared using t-test. For the digital photometric method,
t-test was also performed on the results from two different
digital cameras, two different software for calculating
RGB values, and two different methods of computing
for concentrations.
RESULTS AND DISCUSSION
Visible spectrophotometry
The steel samples for the spectrophotometric determination
of chromium and manganese were prepared by oxidation
with acid and persulfate. The steel samples were placed in
concentrated sulfuric acid in order to dissolve chromium
metal and in nitric acid to dissolve manganese metal.
The dissolution was followed by further oxidation of
chromium to dichromate and manganese to permanganate.
Further oxidation of Cr3+ to hexavalent chromium was
carried out in the experiment. The oxidation to dichromate
by persulfate was catalyzed by silver nitrate.
Before analysis, the wavelengths of maximum absorption
for permanganate and dichromate were determined by
taking separate spectral scans of each sample solution
containing permanganate or dichromate from 400nm
to 800nm using the visible spectrophotometer. Based
on the absorption spectra the wavelengths of maximum
absorption ( max) for permanganate and dichromate
were 525nm and 440nm, respectively. These agree
with literature values (Thomas and Burgess 2007). The
absorbances of the prepared permanganate and dichromate
standards were read at the corresponding wavelengths and
then plotted against the concentration of standards in order
to generate the standard plots. Data points with absorbance
values above 1.0 were not included in the plots.
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Vol. 144 No. 2, December 2015
For the permanganate standard solutions, the empirical
regression equations are:
440 nm: y = 99.5 x - 0.003; R2 = 0.994 (3)
525 nm: y = 2213 x - 0.030; R2 = 0.992 (4)
For the dichromate standard solutions, the empirical
regression equations are:
440 nm: y = 386.8 x - 0.005; R2 = 0.998 (5)
525 nm: y = 31.66 x + 0.002; R = 0.996
2
(6)
The slopes of the graphs correspond to the molar
absorptivities () of the absorbing species at the two max.
The absorbances of the unknown samples were determined
at 440 and 525nm which were inputted into equations 1 and
2. The concentrations of permanganate and dichromate in
solution were determined by simultaneously solving these
two equations. Corresponding dilutions were incorporated
and the final permanganate and dichromate concentrations
were converted into content (in % w/w) of each metal in the
steel sample. The calculated results for Mn and Cr contents
of the steel sample are presented in Table 1.
Table 1. Solution concentration and content of Mn and Cr in steel
sample using visible spectrophotometry.
Metal Solution conc., M Metal content , % (w/w)
Manganese 5.4010-4 2.14
Chromium 2.0910-4 1.54
Range of linearity for spectrophotometric method
For visible spectrophotometry, assuming an ideal R2
value of at least 0.990, all concentrations of the standards
fell within the ideal range of linearity since at any
range from 0 to 0.001 and 0.0004M permanganate and
dichromate, respectively, the R2 value registered a value
of at least 0.990.
Initial RGB values at varying analyte concentrations
RGB values of dichromate and permanganate solutions of
varying concentrations were determined. Values of R, G,
and B were plotted individually against the corresponding
dichromate and permanganate concentrations and are
shown in Figure 1. In the RGB plots for permanganate
solutions, the G values showed a downward trend that
was linear at dilute concentrations. However, the R
and B values were relatively constant and were similar
which averaged 155.8 9.7. For dichromate solutions,
the G value showed the same trend as the B value for
permanganate solutions. The average R and G values were
161.1 11.1 and 151.6 250 3.9, respectively.
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Vedad et al: Cr and Mn contents of steel
determined by digital photometry
Digital photometry using 10-MP camera and linear
G-B plots
Digital still photographs of the standard permanganate
and dichromate solutions were taken using the 10-MP
digital camera. The RGB values were determined using
two free-access software namely SI ColorPicker and RGB
Analysis of Image Colors. Surface plots of the R, G, and
B values were generated using these two software.
Consistent with the initial survey of RGB values of
standard solutions containing only permanganate or
only dichromate, the RGB values of standard solutions
containing both permanganate and dichromate showed
similar trends. The average R value was 175.8 9.4
from the RGB Analysis of Image Colors and 175.0 9.6
from the SI ColorPicker. The G values decreased with
increasing permanganate concentrations but remained
constant with increasing dichromate concentration.
The B surface plots showed no significant variation in
the B value with varying permanganate concentration.
However, the B value decreased with increasing dichromate
concentrations showing a constant blue component
contribution of permanganate over the range of dichromate
concentrations. From both G and B surface plots, the G and
B values were averaged and plotted against permanganate
and dichromate concentrations, respectively, and curved
plots were generated (Fig. 1). The plots were approximated
by a straight line at very low concentrations of the analyte.
The concentration range for linearity was based on a
minimum value of 0.95 for the regression coefficient (R2).
From the R2 values determined at different concentration
ranges for both G and B plots, the maximum concentration
where linear approximation is valid was found to be 0.005M
for permanganate and 0.0028M for dichromate. The lowest
six concentrations, all of which are less 12 than the above-
mentioned maximal concentrations, were included in the
linear extrapolation for uniformity.
Standard linear plots of G and B were then constructed
for the determination of unknown concentrations of the
two dissolved metals. Using linear regression analysis,
equations of the linear approximations were generated.
These generated linear equations were used to calculate
the unknown analyte concentrations. Unknown samples
were analyzed at a final dilution of 1:2. The calculated
permanganate solution concentration and manganese
content of steel samples are presented in Table 2. The
corresponding results for dichromate concentration and
chromium content of steel samples are given in Table 3.
Limit of detection from G and B plots using 10-MP camera
The concentration limit of detection Clod of permanganate
was determined from extrapolated linear plots of G
values versus the lowest permanganate concentrations.
It was calculated by dividing the standard error of the
Philippine Journal of Science
Vol. 144 No. 2, December 2015
(b)
Figure 1. Plots of R, G, and B values of solutions against concentration of (a) permanganate and (b) dichromate.
extrapolated regression line (after multiplication by
three) by the slope of the line (Stone and Ellis 2006).
The corresponding Clod value of dichromate was similarly
determined except that B (instead of G) values were
used. The calculated Clod values for permanganate and
Vedad et al: Cr and Mn contents of steel
determined by digital photometry
dichromate are summarized in Table 4. It can be seen in
Table 4 that the RGB Analysis of Image Colors software
has slightly lower values of Clod, and is able to detect
lower analyte concentrations, compared to SI ColorPicker
software for both permanganate and dichromate.
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Vol. 144 No. 2, December 2015 determined by digital photometry

Table 2. Calculated permanganate solution concentration and manganese content of steel sample using 10-MP camera.

RGB Analysis of Image Colors SI ColorPicker

Trial
KMnO4 Mn content KMnO4 Mn content
G G
conc., M % (w/w) conc., M % (w/w)
1 86 5.4110-4 2.14 85 5.4610-4 2.16

2 87 5.3310-4 2.11 86 5.3710-4 2.12

3 86 5.4110-4 2.14 86 5.3710-4 2.12

Average 2.13 2.13

Standard Deviation 0.02 0.02

Table 3. Calculated dichromate solution concentration and chromium content of steel sample using 10-MP camera.

RGB Analysis of Image Colors SI ColorPicker

Trial
K2Cr2O7 Cr content K2Cr2O7 Cr content
B B
conc., M % (w/w) conc., M % (w/w)

1 148 2.2210-4 1.64 148 5.4610-4 1.72

2 149 1.8810-4 1.38 149 5.3710-4 1.48

3 148 2.2210-4 1.64 148 5.3710-4 1.72

Average 1.55 1.64

Standard Deviation 0.15 0.15

Digital photometry using 10-MPcamera and a* - b* plots The a* was found to be relatively constant in surface plots
Using the same RGB data as in the previous section, values of a* and b* values as dichromate concentration was varied.
of a* (degree of greenness) and b* (degree of blueness) The standards with zero permanganate concentration had
were calculated using the following equations where initial negative a* values and addition of permanganate increased
RGB values were first converted to linear RGB (R,G and and made the a* values positive. A hyperbolic increase
B) using the formulas: in a* values was observed with increasing permanganate
concentration. For the b* surface plots, a hyperbolic
R=(R/255)2.2 (7a) increase and an exponential drop in b* were observed,
G=(G/255)2.2 (7b) respectively, with increasing permanganate and dichromate
B=(B/255)2.2 (7c) concentrations. These opposite trends prevented the use of
The linear RGB values were then converted to XYZ values simple linear approximations to describe the surface plots.
using the formulas: The a* values were linearly approximated at dilute
X=0.3933R+0.3651G+0.1903B (8a) permanganate concentrations and the linear range of the
Y =0.2123R+0.7010G+0.0858B (8b) a* plots was determined (Figure 2). An R2 value of at least
Z=0.0182R+0.1117G+0.9570B (8c) 0.980 was assumed to be ideal for linear approximation.
Concentrations above 0.0004M permanganate were
Finally, the XYZ values were converted to a* and b* rejected for the linear approximation. The a* values for
values: the unknowns were calculated and the permanganate
concentrations were determined by interpolating the
=500 (9)
computed a* value in the linear plots.
The Table Curve 3D version 4.0 software was used to
=200 (10)
generate an equation for the b* surface plot. The selected
equation was in the form
where Xn = 0.98072; Yn = 1.0000; Zn = 1.1823
=+ ln+ (11)

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Vol. 144 No. 2, December 2015 determined by digital photometry

Figure 2. Standard calibration plots generated using a* values from (a) RGB Analysis of Image Colors and (b)
SI ColorPicker.

where x= permanganate concentration Comparison of the two computer software

y= dichromate concentration
z= b* value
a, b and c are constants
The values of the constants were also determined using
the same software. The dichromate concentration was
calculated using as inputs the previously calculated
permanganate concentration and the calculated b* from
the RGB data.
T-test at 95% confidence level was performed on the
concentrations determined using RGB Analysis of Image
Colors and SI ColorPicker. The comparison was done
for both sets of data using the 10-MP Nikon and 12-MP
Olympus digital cameras. The calculated concentrations
of manganese and chromium from the plots of a*
versus concentration are summarized in Tables 5 and 6,
respectively.

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Vol. 144 No. 2, December 2015 determined by digital photometry

Table 4. Calculated concentration limits of detection using the G -B
plot method of computing analyte concentrations.
RGB Analysis of
SI ColorPicker
Image Colors
KMnO4 1.1910-4 M 1.3210-4 M
K2Cr2O7 1.7010-4 M 2.5610-4 M
At 95% confidence level, there were no significant differences
between computed Mn and Cr concentrations computed from
the G and B plot method from RGB data using the RGB
Analysis of Image Colors and the SI ColorPicker. T-test at
95% confidence level was also performed on concentrations
calculated from the a* and b* plots.
There were no other significant differences between
measurements using RGB Analysis of Image Colors data
and the SI ColorPicker data with respect to concentrations
calculated using the a* and b* plots. From this information,
it can be said that RGB values generated from the RGB
Analysis of Image Colors and the SI ColorPicker are
statistically the same; either software gave the same RGB
value for a certain sample.
Comparison of concentrations using 10-MP and 12-
MP cameras
T-test was performed to determine differences in the
calculated concentrations and corresponding metal contents
using data from the 10-MP and 12- MP cameras at 95%
confidence level. The final results are presented in Table
7. No significant differences between the 10- and 12-MP
camera data were observed at 95%confidence level using
the G-B plot method. For the a*-b* method, there were
significant differences in the computed manganese contents
while no significant differences were observed between the
chromium values. The results indicate that the G-B plot
method gave consistent results regardless of resolution of
the camera. On the other hand, the a*-b* plot method did
not give consistent results; it was a less reliable method of
calculation and depended on camera resolution.
Comparison of methods using G-B and a*- b* plots
T-test showed that there were no significant differences in
permanganate and dichromate concentrations determined
using the G - B and a* - b* plots, as shown in Tables 5
and 6.
Comparison of the two photometric methods
The computed manganese and chromium contents
of the steel sample using digital photometric data

Table 5. Permanganate concentration and Mn content computed using a* plots for the 10-megapixel digital camera.
RGB Analysis of Image Colors SI ColorPicker

Trial a* KMnO4 conc, M Mn content % (w/w) a* KMnO4 conc, M Mn content % (w/w)

1 37.70 5.8210-4 2.30 38.27 5.8410-4 2.31

2 37.31 5.7810-4 2.28 38.19 5.8310-4 2.31

3 37.39 5.7910-4 2.29 37.70 5.7710-4 2.28

Average 2.29 2.30

Standard Deviation 0.01 0.01

Table 6. Dichromate concentration and Cr content computed using b* plots for the 10-megapixel digital camera.

RGB Analysis of Image Colors SI ColorPicker

Trial K2Cr2O7 K2Cr2O7 Cr Content

b* Cr Content % (w/w) b*
Concentration, M Concentration, M % (w/w)

1 18.80 1.8310-4 1.35 19.16 1.7210-4 1.27

2 19.01 1.7710-4 1.30 19.12 1.7310-4 1.27

3 19.04 1.7710-4 1.30 18.81 1.7810-4 1.31

Average 1.32 1.28

Standard Deviation 0.03 0.02

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Vol. 144 No. 2, December 2015 determined by digital photometry

Table 7. Comparison of Mn and Cr contents using 10-MP and 12-MP cameras.

10-MP NIKON
Metal Content 12-MP OLYMPUS FE-46 Significant Difference?
Coolpix L20

RGB Analysis of Image Colors

Mn, %(w/w) 2.290.02 2.490.04 Yes

Cr, %(w/w) 1.320.03 1.590.11 No

SI ColorPicker
Mn, %(w/w) 2.300.01 2.450.02 Yes

Cr, %(w/w) 1.280.02 1.420.11 No

Table 8. Comparison of results of Mn and Cr analysis from digital photometry and visible spectrophotometry.
Method of Metal content Significant
Digital Camera Software Analyte
Calculation %(w/w) Difference?
RGB Mn 2.130.02 No
Analysis of Image
10-MP NIKON Colors Cr 1.550.15 No
Coolpix L20 Mn 2.130.02 No
SI
ColorPicker Cr 1.640.15 No
RGB Mn 2.100.02 No
G - B Plot Method Analysis of Image
Colors Cr 1.520.29 No
12-MP OLYMPUS
FE-46 SI Mn 2.110.02 No
ColorPicker Cr 1.570.17 No
RGB Mn 2.190.02 Yes
Analysis of Image
10-MP NIKON Colors Cr 1.320.03 Yes
Coolpix L20
SI Mn 2.300.01 Yes
ColorPicker Cr 1.280.02 Yes
RGB Mn 2.490.04 Yes
a* - b* Plot Method Analysis of Image
Colors Cr 1.590.11 No
12-MP OLYMPUS
FE-46 SI Mn 2.450.02 Yes
ColorPicker Cr 1.420.11 No

were compared with those obtained using visible
spectrophotometry. Using t-test, significant differences
between the two methods were observed. These are
summarized in Table 8. The G - B plot method of
digital photometry gave analytical results which were
not significantly different from the spectrophotometric
results. In comparison, using the a* - b* plot method
only the chromium contents obtained with the 12-MP
camera passed the t-test. Therefore, between the G - B
plot and a* - b* plot methods of computation, the first
is preferred for greater accuracy which is comparable
to that of visible spectrophotometry.
Precision of digital photometric method
Duplicate experiments were done in two succeeding
days employing the selected computational method for
analyte concentration using the same steel sample. The
calculated analyte concentrations and corresponding
metal contents were compared by t-test and the results are
presented in Table 9. After repeating the experiment and
computing the concentrations, as well as corresponding
metal contents from the RGB data using the G - B plot
method, no significant differences were observed from the
results of the two experiments. This shows that the digital
photometric method gave reproducible results.

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Vol. 144 No. 2, December 2015 determined by digital photometry

Accuracy of digital photometry CONCLUSION

Comparison of the calculated concentration using the
selected method for calculation (G-B plot method) with
the theoretical concentrations of 0.00025M KMnO4 and
0.001M K2Cr2O7 showed that there were no significant
differences between any of the calculated concentrations.
Furthermore, the concentrations obtained from visible
spectrophotometry showed no significant differences with
the theoretical concentrations (Tables 10 and 11).
Based on the results, the G -B plot of digital photometry
was found to be accurate for calculating permanganate and
dichromate concentrations using 10- or 12-MP digital camera.
Digital photometry was used to determine unknown
contents of chromium and manganese in steel after being
dissolved and oxidized in order to have the manganese
and chromium in permanganate and dichromate forms,
respectively.
Simultaneous analysis by visible spectrophotometry
was also done on the prepared steel samples. The G
(green) and B (blue) values were observed to decrease
with increasing concentrations of permanganate and
dichromate, respectively, until the G and B values became

Table 9. Assessment of inter-day precision based on calculated metal contents.

Metal content, %(w/w) Significant

Digital Camera Software Analyte
Exp 1 Exp 2 Difference?

Mn 2.130.02 2.140.02 No
RGB Analysis of Image Colors
10-MP NIKON Cr 1.550.15 1.510.26 No
Coolpix L20 Mn 2.130.02 2.140.00 No
SI ColorPicker
Cr 1.640.15 1.500.15 No

Mn 2.100.02 2.140.02 No
RGB Analysis of Image Colors
Cr 1.520.29 1.510.26 No
12-MP OLYMPUS
FE-46 Mn 2.110.02 2.110.04 No
SI ColorPicker
Cr 1.570.17 1.550.17 No

Table 10. Evaluation of accuracy for spectrophotometric and digital photometric methods based on calculated
permanganate concentration of a known solution.
KMnO4
Method
Concentration, M Standard Deviation Significant Difference?

Vis Spectrophotometry 2.5210-4 2.7610-6 No

10-MP RGB AIC 2.5010 -4

2.4310-6
No
Camera SI ColorPicker 2.4510-4 4.1910-6 No

RGB AIC 2.5910-4 3.1410-6 No

12-MP
Camera SI ColorPicker 2.4510 -4
5.4710-6
No

Table 11. Evaluation of accuracy for spectrophotometric and digital photometric methods based on calculated
dichromate concentration of a known solution.
K2Cr2O7
Method
Concentration, M Standard Deviation Significant Difference?
Vis Spectrophotometry 1.0010 -3
2.4910 -6
No

10-MP RGB AIC 0.9910 -3

1.0210 -5
No
Camera SI ColorPicker 1.0010 -3
1.0310 -5
No

12-MP RGB AIC 1.0310 -3

1.1710 -5
No
Camera SI ColorPicker 1.0610 -3
2.0110 -5
No

126
Philippine Journal of Science Vedad et al: Cr and Mn contents of steel
Vol. 144 No. 2, December 2015 determined by digital photometry

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