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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


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

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Philippine Journal of Science Vedad et al: Cr and Mn contents of steel
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The concentration of colored solutes is commonly commercially available stainless steel and used as sample
determined using a visible spectrophotometer. Alternatively, for determination of chromium and manganese.
a digital camera may be used to take photographs of the
solutions and color analysis of the photographs may be
Equipment
used in order to calculate the concentration of colored
A Shimadzu Mini 1240 Spectrophotometer was used for
species (after suitable calibration with standard solutions).
spectrophotometric measurements. Digital photographic
This digital photometric method is based on colorimetry
data were gathered using two digital cameras: 12
which quantifies the human color perception using the
megapixel Olympus FE-46 and 10 megapixel Nikon
International Commission for Illumination (CIE) system
Coolpix L20. For RGB analysis, a laptop computer with
(CIE 2004). This system uses a chromaticity diagram, for
Windows XP operating system was used after installing
the representation of perceived colors. The RGB model
Java applet RGB Analysis of Image Colors and SI
describes the amounts of the primary colors red (R), green
ColorPicker software. The generation of surface equations
(G), and blue (B) that contribute to the color of the image.
was done using the TableCurve 3D version 4.0, also
The RGB values may be represented by different notations:
installed in the same computer.
the arithmetic, percentage, digital 8-bit per channel and
digital 26-bit per channel.
Sample preparation
Few analytical methods for chemical analysis based on digital One gram of steel sample was weighed and placed in
photometry have been developed. One innovation in this a 250-mL beaker into which deionized water (50 mL),
field involves tristimulus colorimetry that uses RGB values concentrated sulfuric acid (10 mL) and concentrated
derived from digital photographic data. The RGB values, phosphoric acid (5 mL) were added. The mixture was
after transformation into measures of redness-greenness heated for at least half an hour at 80-90 degrees C until
and yellowness-blueness, have been applied to the analysis effervescence ceased. Concentrated nitric acid (5 mL)
of iron and residual chlorine in water (Suzuki, et al. 2006). was added after cooling the mixture, which was heated
RGB color analysis has also been applied to blood glucose again until the steel sample completely dissolved. The
determination (Raja and Sankaranarayanan 2007) and soluble resulting solution, after cooling, was transferred into
protein concentration (Yanos et al. 2013). The RGB Analysis a 250-mL volumetric flask, diluted to the mark with
of Color Image, which is a Java Applet available from the deionized water, and then filtered in order to remove any
Internet, allows the determination of RGB values of a given undissolved impurities. A 25-mL aliquot of the solution
area of a digital still photograph. It was initially applied to was transferred into an Erlenmeyer flask and 5 mL each
the study of insect colors in order to accurately duplicate of concentrated solutions of sulfuric acid and phosphoric
them from the generated RGB values (Byers 2006). The SI acid were added. One mL of 1M silver nitrate solution was
ColorPicker, which is also freely downloadable from the then added followed by 5 g of potassium metapersulfate.
Internet, is a similar computer software that presents RGB The mixture was swirled and then heated to boiling for five
values in decimal format. However, it calculates RGB values minutes. The mixture was cooled slightly and potassium
per pixel and not per area of the photograph. metaperiodate (0.5 g) was added. The mixture was heated
The present study deals with the application of digital again to gentle boiling for 5 minutes and then diluted to
photometry to the simultaneous analysis of chromium 50 mL with deionized water. Three trials were performed.
and manganese in steel after converting the metals into
dichromate and permanganate, respectively. A digital Visible spectrophotometric determination
camera was used to take still photographs of the colored A set of standard solutions of KMnO4 and K2Cr2O7 was
solutions. Color analysis of the digital photographs was prepared with concentrations in the range of 1.0 - 1010-4 M
done using two software downloaded from the Internet, (in increments of 1.010-4 M) for permanganate standards
namely RGB Analysis of Color Image and SI ColorPicker. and 4.0 - 4010-4 M (in increments of 4.010-4 M) for
The results were compared in accuracy and reproducibility dichromate standards. The standard solutions were
with those using conventional visible spectrophotometry. 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
MATERIALS AND METHODS were done and the wavelengths of maximum absorption
(c) were determined.
Reagents and chemicals The absorbances of the standard solutions were determined
All chemicals used in the experiments are reagent at the corresponding values of max for KMnO4 and
grade from Sigma-Aldrich. Filings were prepared from K 2 Cr 2 O 7 . The absorbance of each solution at the

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

appropriate max was plotted versus concentration. The Validation of accuracy


molar absorptivities () at the two wavelengths for both The accuracy of the photometric method for determining
compounds were determined using the Beer-Lamberts manganese and chromium was validated by analyzing a
Law. The absorbances of the steel samples were measured solution containing known concentrations of permanganate
at the corresponding max and the concentrations of KMnO4 and dichromate using both visible spectrophotometry and
and K2Cr2O7 in these solutions were determined using the digital photometry.
following equations:
Using reagent grade potassium permanganate and
1= 1, + 1, (1) potassium dichromate, a solution with final permanganate
4 4 2 2 7 2 2 7
and dichromate concentrations of 0.00025M and
2=2, + 2, (2) 0.001M, respectively, was prepared with final sulfuric
4 4 2 2 7 2 2 7
acid concentration of 0.5M. The prepared solution was
analyzed using visible spectrophotometry and digital
Digital photometric analysis photometry and three trials were done. Results of both
Two 15-watt fluorescent bulbs were placed 21.6 cm methods were compared with the theoretical value.
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 Statistical analyses of results
plastic polymer with ten palette wells each containing The concentrations determined using both visible
0.5 mL of analyte solution. The digital photometric spectrophotometric and digital photometric methods were
set-up has been described with a drawing in a previous compared using t-test. For the digital photometric method,
publication from the authors laboratory (Yanos et al. t-test was also performed on the results from two different
2013). It was placed in a dark room where no other light digital cameras, two different software for calculating
source was available. The flash feature of the camera RGB values, and two different methods of computing
was deactivated. for concentrations.

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 RESULTS AND DISCUSSION
increments of 0.810-3 M) were prepared. Photographs
of these solutions were taken in the experimental set-up Visible spectrophotometry
using the 10 megapixel Nikon Coolpix L20 digital camera. The steel samples for the spectrophotometric determination
The RGB values were determined using the software RGB of chromium and manganese were prepared by oxidation
Analysis of Image Colors. with acid and persulfate. The steel samples were placed in
Standard solutions of KMnO 4 and K 2 Cr 2 O 7 were concentrated sulfuric acid in order to dissolve chromium
prepared with concentrations mentioned above and metal and in nitric acid to dissolve manganese metal.
1:1 (v/v) mixtures of these standard solutions were The dissolution was followed by further oxidation of
prepared, as well as the blank, with a final H 2SO 4 chromium to dichromate and manganese to permanganate.
concentration of 0.5M. The mixed standard solutions Further oxidation of Cr3+ to hexavalent chromium was
(0.5 mL each) were placed in white palette wells and carried out in the experiment. The oxidation to dichromate
digital still photographs were taken with the two digital by persulfate was catalyzed by silver nitrate.
cameras using the timer mode. A digital still photograph Before analysis, the wavelengths of maximum absorption
of the unknown sample was also taken using the same for permanganate and dichromate were determined by
set-up and camera settings. taking separate spectral scans of each sample solution
The digital still photographs were analyzed by determining containing permanganate or dichromate from 400nm
the RGB values for each standard and sample using the to 800nm using the visible spectrophotometer. Based
RGB Analysis of Image Colors (Byers 2006). on the absorption spectra the wavelengths of maximum
absorption ( max) for permanganate and dichromate
were 525nm and 440nm, respectively. These agree
Test for repeatability with literature values (Thomas and Burgess 2007). The
The digital photometric analysis of the steel sample was absorbances of the prepared permanganate and dichromate
repeated in order to determine its intra-day precision using standards were read at the corresponding wavelengths and
the same equipment and doing the duplicate analysis on then plotted against the concentration of standards in order
the same date by the same analyst. The results of the to generate the standard plots. Data points with absorbance
second analysis were compared with the earlier results. values above 1.0 were not included in the plots.

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Philippine Journal of Science Vedad et al: Cr and Mn contents of steel
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For the permanganate standard solutions, the empirical Digital photometry using 10-MP camera and linear
regression equations are: G-B plots
Digital still photographs of the standard permanganate
440 nm: y = 99.5 x - 0.003; R2 = 0.994 (3) and dichromate solutions were taken using the 10-MP
525 nm: y = 2213 x - 0.030; R2 = 0.992 (4) digital camera. The RGB values were determined using
two free-access software namely SI ColorPicker and RGB
For the dichromate standard solutions, the empirical Analysis of Image Colors. Surface plots of the R, G, and
regression equations are: B values were generated using these two software.
440 nm: y = 386.8 x - 0.005; R2 = 0.998 (5) Consistent with the initial survey of RGB values of
525 nm: y = 31.66 x + 0.002; R = 0.996
2
(6) standard solutions containing only permanganate or
only dichromate, the RGB values of standard solutions
The slopes of the graphs correspond to the molar containing both permanganate and dichromate showed
absorptivities () of the absorbing species at the two max. similar trends. The average R value was 175.8 9.4
The absorbances of the unknown samples were determined from the RGB Analysis of Image Colors and 175.0 9.6
at 440 and 525nm which were inputted into equations 1 and from the SI ColorPicker. The G values decreased with
2. The concentrations of permanganate and dichromate in increasing permanganate concentrations but remained
solution were determined by simultaneously solving these constant with increasing dichromate concentration.
two equations. Corresponding dilutions were incorporated
and the final permanganate and dichromate concentrations The B surface plots showed no significant variation in
were converted into content (in % w/w) of each metal in the the B value with varying permanganate concentration.
steel sample. The calculated results for Mn and Cr contents However, the B value decreased with increasing dichromate
of the steel sample are presented in Table 1. 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
Table 1. Solution concentration and content of Mn and Cr in steel B values were averaged and plotted against permanganate
sample using visible spectrophotometry.
and dichromate concentrations, respectively, and curved
Metal Solution conc., M Metal content , % (w/w) plots were generated (Fig. 1). The plots were approximated
Manganese 5.4010-4 2.14
by a straight line at very low concentrations of the analyte.
The concentration range for linearity was based on a
Chromium 2.0910-4 1.54 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
Range of linearity for spectrophotometric method where linear approximation is valid was found to be 0.005M
For visible spectrophotometry, assuming an ideal R2 for permanganate and 0.0028M for dichromate. The lowest
value of at least 0.990, all concentrations of the standards six concentrations, all of which are less 12 than the above-
fell within the ideal range of linearity since at any mentioned maximal concentrations, were included in the
range from 0 to 0.001 and 0.0004M permanganate and linear extrapolation for uniformity.
dichromate, respectively, the R2 value registered a value
of at least 0.990. 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,
Initial RGB values at varying analyte concentrations
equations of the linear approximations were generated.
RGB values of dichromate and permanganate solutions of
These generated linear equations were used to calculate
varying concentrations were determined. Values of R, G,
the unknown analyte concentrations. Unknown samples
and B were plotted individually against the corresponding
were analyzed at a final dilution of 1:2. The calculated
dichromate and permanganate concentrations and are
permanganate solution concentration and manganese
shown in Figure 1. In the RGB plots for permanganate
content of steel samples are presented in Table 2. The
solutions, the G values showed a downward trend that
corresponding results for dichromate concentration and
was linear at dilute concentrations. However, the R
chromium content of steel samples are given in Table 3.
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 Limit of detection from G and B plots using 10-MP camera
permanganate solutions. The average R and G values were The concentration limit of detection Clod of permanganate
161.1 11.1 and 151.6 250 3.9, respectively. was determined from extrapolated linear plots of G
values versus the lowest permanganate concentrations.
It was calculated by dividing the standard error of the

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(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 dichromate are summarized in Table 4. It can be seen in
three) by the slope of the line (Stone and Ellis 2006). Table 4 that the RGB Analysis of Image Colors software
The corresponding Clod value of dichromate was similarly has slightly lower values of Clod, and is able to detect
determined except that B (instead of G) values were lower analyte concentrations, compared to SI ColorPicker
used. The calculated Clod values for permanganate and software for both permanganate and dichromate.

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

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Table 4. Calculated concentration limits of detection using the G -B Comparison of concentrations using 10-MP and 12-
plot method of computing analyte concentrations. MP cameras
RGB Analysis of
T-test was performed to determine differences in the
SI ColorPicker calculated concentrations and corresponding metal contents
Image Colors
using data from the 10-MP and 12- MP cameras at 95%
KMnO4 1.1910-4 M 1.3210-4 M confidence level. The final results are presented in Table
K2Cr2O7 1.7010-4 M 2.5610-4 M 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
At 95% confidence level, there were no significant differences significant differences in the computed manganese contents
between computed Mn and Cr concentrations computed from while no significant differences were observed between the
the G and B plot method from RGB data using the RGB chromium values. The results indicate that the G-B plot
Analysis of Image Colors and the SI ColorPicker. T-test at method gave consistent results regardless of resolution of
95% confidence level was also performed on concentrations the camera. On the other hand, the a*-b* plot method did
calculated from the a* and b* plots. not give consistent results; it was a less reliable method of
calculation and depended on camera resolution.
There were no other significant differences between
measurements using RGB Analysis of Image Colors data
and the SI ColorPicker data with respect to concentrations Comparison of methods using G-B and a*- b* plots
calculated using the a* and b* plots. From this information, T-test showed that there were no significant differences in
it can be said that RGB values generated from the RGB permanganate and dichromate concentrations determined
Analysis of Image Colors and the SI ColorPicker are using the G - B and a* - b* plots, as shown in Tables 5
statistically the same; either software gave the same RGB and 6.
value for a certain sample.
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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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 Precision of digital photometric method
spectrophotometry. Using t-test, significant differences Duplicate experiments were done in two succeeding
between the two methods were observed. These are days employing the selected computational method for
summarized in Table 8. The G - B plot method of analyte concentration using the same steel sample. The
digital photometry gave analytical results which were calculated analyte concentrations and corresponding
not significantly different from the spectrophotometric metal contents were compared by t-test and the results are
results. In comparison, using the a* - b* plot method presented in Table 9. After repeating the experiment and
only the chromium contents obtained with the 12-MP computing the concentrations, as well as corresponding
camera passed the t-test. Therefore, between the G - B metal contents from the RGB data using the G - B plot
plot and a* - b* plot methods of computation, the first method, no significant differences were observed from the
is preferred for greater accuracy which is comparable results of the two experiments. This shows that the digital
to that of visible spectrophotometry. photometric method gave reproducible results.

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Accuracy of digital photometry CONCLUSION


Comparison of the calculated concentration using the
selected method for calculation (G-B plot method) with Digital photometry was used to determine unknown
the theoretical concentrations of 0.00025M KMnO4 and contents of chromium and manganese in steel after being
0.001M K2Cr2O7 showed that there were no significant dissolved and oxidized in order to have the manganese
differences between any of the calculated concentrations. and chromium in permanganate and dichromate forms,
Furthermore, the concentrations obtained from visible respectively.
spectrophotometry showed no significant differences with Simultaneous analysis by visible spectrophotometry
the theoretical concentrations (Tables 10 and 11). was also done on the prepared steel samples. The G
Based on the results, the G -B plot of digital photometry (green) and B (blue) values were observed to decrease
was found to be accurate for calculating permanganate and with increasing concentrations of permanganate and
dichromate concentrations using 10- or 12-MP digital camera. 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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of Image Colors and SI ColorPicker. Two methods of html on 18 September 2015
computing the concentrations were employed, namely G
SUZUKI Y, ENDO M, JIN J, IWASE K, IWATSUKI
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M. 2006. Tristimulus colorimetry using a digital still
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YANOS AA, BAUTISTA MN, ANGELIA MRN, DEL
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of protein using biuret, Bradford, and bicinchoninic
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that uses a relatively inexpensive digital camera for the
simultaneous determination of chromium and manganese
in steel samples.

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