Journal of Ocean University of China (Oceanic and Coastal Sea Research)

ISSN 1672-5182, April 30, 2006, Vol.5, No.2, pp.137-140

http: // www. ouc. edu. cn/xbywb/
E-maih xbywb@mail, ouc edu. cn

A New Spectrophotometric Method for Measuring

COD of Seawater
LIU Ying, JI Hongwei~, XIN Huizhen, and LIU Li
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education,
Ocean University of China, Qingdao 266003, P. R. China

(Received January 26,2005 ; accepted December 14, 2005)

Abstract This research studied a new spectrophotometric method for measuring the chemical oxygen demand (COD) of
seawater. In this method, the COD was measured using a spectrophotometer instead of titrating with sodium thiosulphate.
The measuring wavelength was selected to be 470 nm, and the COD of three standard glucose solutions (COD = 0.5, 1.5 and
2.5 mgL 1, respectively) and two seawater samples (from the South Yellow Sea and Jiaozhou Bay) were measured using the
spectrophotometric method and titrimetric method respectively. The results showed that the spectrophotometric method was

somewhat better than the titrimetric method. The relative standard deviation (RSD) of the spectrophotometric method was
less than 2.7%, and the recovery of seawater samples ranged from 96.3% to 103.8%. In addition, the spectrophotometric
method has other advantages such as expeditiousness, operation simplicity, analysis automatization, etc. Therefore the spectrophotometric method can be used to measure the COD of seawater with satisfactory results.
Key words

chemical oxygen demand (COD); spectrophotometric method; seawater

1 Introduction
Chemical oxygen demand (COD) is defined as the
amount of oxygen equivalents consumed in oxidizing
the organic compounds of samples by strong oxidizing
agents such as dichromate or permanganate. It can reflect the pollution degree of water and is one of the
most important parameters to assess pollution in water
monitoring (Huang, 1989; Zhang, 1989).
At present, the COD of freshwater is usually measured using titrimetric method after oxidization by
dichromate or acidic permanganate, and that of seawater using titrimetric method after oxidization by
permanganate in alkaline condition ( F u and Xu,
1997; Administration of Quality and Technical Supervision of the People's Republic of China, 1999). Because the titrimetric method has some drawbacks,
such as unsteadiness of sodium thiosulphate, high consumption of chemicals, long analysis time, impossibility of automatic measurement, e t c , new analytical
methods have been developed. Now some spectrophotometric methods are used to measure the COD in
freshwater and urban and industrial waste water systems (Chen and Cheng, 2002; Sibel, 2003; Houda,
1999; Wang and Liang, 2000; Zhu and Zeng, 2003;
State Environmental Protection Administration of China, 1989). However, there have been few reports on
Corresponding author. Teh0086-532-82032482-8122
E-mail: hwji@mail. ouc. edu. cn

measuring COD of seawater using spectrophotometric

method. For example, Xu and Zhang ( 2 0 0 3 ) measured COD in seawater by measuring the absorbance of
permanganate, mainly investigating the influence of
medium acidity and the measuring time interval. This
research was designed to develop a new spectrophotometric method of determining COD of seawater by
measuring the absorbance of I2 standard solution
rather than that of permanganate. The results showed
that this new spectrophotometric method is suitable
for the measurement of COD of seawater.

2 Materials and Methods

2.1

Apparatus

and Reagents

The model o{ the U V - V I S spectrophotometer is

HP8453 of Agilent Co.
The iodine used was guarantee grade and the other
chemicals were all of analytical grade. The analytical
solutions were prepared according co the national standard ( T h e Administration of Quality and Technical
Supervision of the People's Republic of China, 1999).
COD standard solution:
First, 0.234 3 g glucose (dried at 60 - 70 ~ for 2 h
prior to use) was dissolved in redistilled water and adjusted to a final volume of 500 mL. T h e theoretical
COD of this solution was 500 m g L -1. Then, 1.0 mL,
3.0 m L and 5.0 m L of this solution were diluted to
1 000 mL respectively, and three glucose standard solutions with COD of 0.5, 1.5 and 2.5 mgL -1 respectiv-

Journal of Ocean University of China

138

ely were obtained.

Potassium hydrogen phthalate ( KCsHsO 4 ) was
dried for 2 h at 105 0(2 and 0.425 1 g of it was dissolved
in redistilled water and adjusted to 1000 mL. The theoretical COD of this solution was 500 m g L -1 . Subsequently, 1.0 mL, 3.0 m L and 5.0 m L of this solution
were diluted to 1 000 m L respectively, and 3 potassium hydrogen phthalate standard solutions with COD
of 0.5, 1.5 and 2.5 m g L -1 respectively were obtained
(Zhang and Liu, 2003).
2 . 2 Methods
2.2.1

Titrimetric method

Vol. 5, No. 2, 2006

where m is the concentration of sodium thiosulphate

(molL 1 ), V1 is the volume of sodium thiosulphate
consumed in titrating the blank solution ( m L ) and V2
is the volume of sodium thiosulphate consumed in
titrating the sample solution ( m L ) .
For the spectrophotometric method, the concentration of COD was calculated using the formula COD
( m g L 1) = 160(61C1-VC2), where V is the volume
o f the sample solutions for absorbance measurement
( m L ) , C1 is the concentration of I2 in the blank solution from the calibration curve ( m o l L - I ) , and C2 is
the concentration of I2 in the sample solution from the
calibration curve ( m o l L - I ) .

The titrimetric method was the same as stipulated

in the national standard ( T h e Administration of Quality and Technical Supervision of the People's Republic
of China, 1999).

3 Results and Discussion

2.2.2

The absorbances of the six I2-KI standard solutions

were read at different wavelengths (400 n m - 510 nm)
with the results shown in Fig. 1 and Table 1.

Spectrophotometric method

First of all, 12.700g I2 and 40.0g K I were dissolved

in 10 L of distilled water, yielding an I2-KI standard
solution ( 0 . 0 0 5 m o l L - i ) . Then, 1.0 mL, 2.0 mL,
3.0 mL, 4.0 mL, 5.0 m L and 6.0 m L of such solution
were transferred into six test tubes respectively, and
were adjusted to 50 mI. with distilled water. The absorbances of these solutions were read on a spectrophotometer at different wavelengths by a 1 cm thick cuvette every 10 nm from 400 nm to 510 nm (Chen,
1997). Distilled water was used as the reference.
Besides, 10.0mL potassium permanganate solution
was transferred into a 250 m L conical flask, in which
0.5 g potassium iodide and 1 m L H 2 S O 4 solution ( 1 : 3 )
were added, and the flask was placed in darkness for
two minutes. 50 m L distilled water was added, the
absorbance of the solution thus formed at the optimal
wavelength was read on a spectrophotometer. The
concentration (C1) of I2 of the blank solution from the
calibration curve was obtained.
The procedure of sample digestion is the same as
stipulated in the standard procedure ( T h e Administration of Quality and Technical Supervision of the
People's Republic of China, 1999). After the digestion step, the absorbance at the selected wavelength
was measured using a spectrophotometer, then the
concentration ( C 2 ) of I2 in the sample solution was
obtained from the calibration curve.
For the titrimetric method, the concentration of
sodium thiosulphate was calculated according to the
formula:
6mKiO3 15.00
lY/Na2S203 --

VNa2S203

the concentration of COD was calculated from the formula

C O D ( m g L -1) = m (V1 - V2) 8/100 1 000

=rn(V1-

V2) x 80,

3 . 1 Determination of the Optimal Wavelength

2.5
2
~ 1.5
~ 1
0.5
0
400 410 420 430 440 450 460 470 480 490 500 510

Wavelength/run
Fig.1 Relationship between absorbance and wavelength of
I2-KI standard solutions.
1. C ( I 2 ) = l . 0 0

2. C ( 1 2 ) = 2 . 0 0

3. C ( l z ) = 3 . 0 0

4molL 1 4. C ( I 2 ) = 4 . 0 0

4molL 1

5. C ( I 2 ) = 5 . 0 0 x 1 0 4molL l; 6. C ( I 2 ) = 6 . 0 0

4molL 1.

Table 1

Absorbances of I2-KI standard solutions

at different w a v e l e n g t h s

Concentrationt/
( 10 -4 molL-I )

Absorbance
450 nm 460 nm

430 nm

440 nm

1.00

0.098

0.094

0.087

0.078

2.00

0.236

0.213

0.185

0.157

0.132

0. 404

0. 354

0. 299

0. 246

0. 199

4.00

0.585

0.506

0.417

0.336

0.266

5.00

0. 774

0. 663

0. 539

0. 428

0. 332

6.00

0. 960

0. 817

0. 658

0. 516

0. 397

3.00

470 nm
0.069

Linear

0.9973

0.9979

0.9988

0.9995

0.9999

Regression
Equation

0.1744

0.1462

0.1153

0.0884

0.0659

0.1010

0.0705

0.0393

0.0158

0.0018

Note: t concentration of the I2-KI standard solutions.

Fig. 1 and Table 1 show that the absorbance of I2K I standard solutions decreases with the increase of
wavelength and there is a good linear relationship between the absorbance and the concentration of I2-KI
from 430 nm to 470 nm, which are in good agreement

L I U Y. et al.: A New Spectrophotometric Method for Measuring COD of Seawater

w i t h t h a t r e p o r t e d previously ( C h e n , 1 9 9 7 ) . T h e line a r i t y ( r = 0.999 9) is the best at 470 n m ; thus 470 n m
was selected as the o p t i m a l w a v e l e n g t h .

3 . 2 Determination of the Standard Substance

P o t a s s i u m h y d r o g e n p h t h a l a t e and glucose were selected as the s t a n d a r d substances, from w h i c h t h e
s t a n d a r d solutions w i t h COD of 0.5, 1.5 and 2.5 m g L 1
w e r e p r e p a r e d respectively. True CODs of those solutions were measured using s p e c t r o p h o t o m e t r i c method. T h e results are listed in Table 2.
Table 2

Oxidizing efficiencies of the standard

solutions of KHP and glucose

CODt/
MeasuredCOD/(mgL 1 )
( mgL - 1)
KHP
Glucose
0.5
-0.29
1.5
0.16
0.78
2.5
0.40
1.29
Note: t COD of standard solutions.

Oxidation efficiency/%
KHP
Glucose
-58.0
10.7
52.0
16.0
51.6

COD of standard/
( mgL -1)

oxidized relatively. W h e n t h e COD of f r e s h w a t e r is

m e a s u r e d b y d i c h r o m a t e or p e r m a n g a n a t e in acidic
conditions, p o t a s s i u m h y d r o g e n p h t h a l a t e is often selected as a s t a n d a r d substance.
But Table 2 suggests t h a t it is not suitable to choose
p o t a s s i u m h y d r o g e n p h t h a l a t e as t h e s t a n d a r d substance w h e n the oxidizing a g e n t is p o t a s s i u m p e r m a n g a n a t e in alkaline conditions. It also shows t h a t even
glucose can not be oxidized c o m p l e t e l y b y alkaline
p o t a s s i u m p e r m a n g a n a t e , t h e o x i d a t i o n efficiency being m e r e l y about 5 1 . 6 % - 5 8 . 0 % and being in accord
w i t h t h a t r e p o r t e d previously ( C h e n and Chen,
1994). T h e r e f o r e w e chose glucose as t h e s t a n d a r d
substance.

3 . 3 Determination of COD of the Standard Solutions

and Seawater Samples

T h e oxidation efficiency of p o t a s s i u m h y d r o g e n p h thalate is much lower t h a n t h a t of t h e glucose. One of

t h e reasons is t h a t p o t a s s i u m h y d r o g e n p h t h a l a t e has a
p h e n y l structure, t h u s can not easily be oxidized b y
p e r m a n g a n a t e in alkaline conditions. O n the o t h e r
hand, glucose has a chain structure, t h u s can be easily
Table 3

139

In o r d e r to verify the reliability of t h e spectrophot o m e t r i c m e t h o d , we m e a s u r e d t h e COD values of t h e

t h r e e glucose s t a n d a r d solutions ( C O D = 0.5, 1.5 and
2.5 m g L -1) and t w o s e a w a t e r samples ( o n e of w h i c h
from Jiaozhou Bay:
2004/07/12,
36~
120~
and the o t h e r from t h e S o u t h Yellow
Sea: 2 0 0 4 / 0 7 / 1 3 , 3 5 ~
120~
b y the
s p e c t r o p h o t o m e t r i c m e t h o d and t h e t i t r i m e t r i c m e t h od. T h e results are listed in Tables 3 and 4.

CODs of glucose standard solutions measured using the two methods

Method+
1

Measured COD/(mgL 1)
3
4

Average

RSD/
%

Oxidation
efficiency/%

0.5

T
SP

0.28
0.28

0.29
0.30

0.29
0.29

0.27
0.30

0.28
0.29

3.4
2.7

56.0
58.0

1.5

T
SP

0.75
0.77

0.79
0.80

0.76
0.78

0.77
0.77

0.77
0.78

2.2
1.8

51.3
52.0

2.5

T
SP

1.26
1.27

1.31
1.30

1.30
1.28

1.27
1.32

1.28
1.29

1.8
1.7

51.2
51.6

Note: t T: titration; SP: spectrophotometry.

Table 4
Samples
The South
Yellow Sea
Jiaozhou Bay

CODs of seawater measured by the two methods

Methodt
T
SP
T
SP

1
0.72
0.77
1.05
1.10

2
0.75
0.74
1.07
1.07

Measured COD/(mgL
3
0.74
0.75
1.04
1.13

1)
4
0.76
0.76
1.10
1.08

RSD/%
Average
0.74
0.76
1.07
1.10

2.3
1.7
2.5
2.4

Note: t T: titration; SP: spectrophotometry.

Tables 3 and 4 s h o w t h a t the average COD values
from the two m e t h o d s are nearly t h e same. A c c o r d i n g
to F - t e s t and T - t e s t analysis (confidence level 95 % ),
t h e r e is no significant difference b e t w e e n t h e t w o
m e t h o d s , b u t the precision of t h e s p e c t r o p h o t o m e t r i c
m e t h o d is s o m e w h a t b e t t e r t h a n t h a t of the t i t r i m e t r i c
m e t h o d . T h e r e f o r e w e can use the s p e c t r o p h o t o m e t r i c
m e t h o d to measure t h e recovery of C O D of s e a w a t e r
by a s t a n d a r d a d d i t i o n e x p e r i m e n t .

3 . 4 The Influence of Volatility of 12 Solution

Because I2 is volatile, t h e absorbance of a single I2
s t a n d a r d solution is not a p p r o p r i a t e for t h e measurem e n t . In o r d e r to p r e v e n t t h e effect of volatility of I2,
K I was a d d e d to improve t h e s t a b i l i t y of I2 as I2 and
K I can p r o d u c e I3- 9 Table 1 s h o w s t h a t t h e calibration
curve was not affected b y t h e volatility of I2. T h e re-

140

Vol. 5, No. 2, 2006

J o u r n a l o f Ocean University o f China

sult is t h e same as t h a t r e p o r t e d previously ( C h e n ,

1997; Z h a n g et al., 2 0 0 3 ) . W e can therefore choose
I2 + K I solutions to measure t h e absorbance.

3 . 5 Recovery of COD of Seawater by a Standard Addition Experiment

F i r s t 1 m L of the s t a n d a r d solutions ( C O D = 50 m g
L -1) were a d d e d into 2 s e a w a t e r samples and t h e n the
COD of t h e t w o samples were m e a s u r e d by the spec-

trophotometric method. The results are listed in Table 5.

Table 3 shows t h a t glucose cannot be oxidized completely b y potassium p e r m a n g a n a t e in alkaline conditions. T h e mean oxidation efficiency is 54.0 % . Therefore t h e oxidation efficiency was t a k e n as 54 % in calculating the recovery, w h i c h was equivalent to an
a d d e d s t a n d a r d substance of 27.00 tag. Table 5 shows
t h a t t h e e x p e r i m e n t a l recovery ranges from 96.3% to
103.8 % , suggesting t h a t the s p e c t r o p h o t o m e t r i c method can be used to m e a s u r e COD of s e a w a t e r .

Table 5
Samples/( 100 rnL)

COD of seawater/
(mgL -1)

The South Yellow Sea

0.76

Jiaozhou Bay

1.09

The results of recovery experiment

COD measured/
COD added//~g
COD recoverd//xg
(mgL 1)
1.01
26.01
27.00
1.03
28.03
(50.00 x 54.0%)
1.02
27.02
27.00

Recovery/%
96.3
103.8
100.1

1.34

26.34

97.6

1.35

27.35

101.3

1.35

27.35

101.3

(50.00

4 Conclusion
T h e e x p e r i m e n t a l results show t h a t 1 ) although
t h e r e is no significant difference b e t w e e n the speet r o p h o t o m e t r i c m e t h o d and the t i t r i m e t r i c m e t h o d at
9 5 % confidence level, the s p e c t r o p h o t o m e t r i c m e t h o d
is s o m e w h a t b e t t e r t h a n t h e t i t r i m e t r i c m e t h o d ; 2 )
the relative s t a n d a r d deviation ( R S D ) of t h e speet r o p h o t o m e t r i c m e t h o d is less t h a n 2 . 7 % and t h e recovery of s e a w a t e r samples ranges from 96.3% to
103.8 % , m e e t i n g t h e r e q u i r e m e n t s of COD measurem e n t of s e a w a t e r ; 3 ) the s p e c t r o p h o t o m e t r i c m e t h o d
has some a d v a n t a g e s over the t i t r i m e t r i c m e t h o d such
as simple d e t e r m i n a t i o n procedure, acceptable precision, a u t o m a t i c analysis, etc; and 4 ) c o m p a r i n g the
results w i t h those r e p o r t e d previously ( X u and Zhang,
2 0 0 3 ) , it can be claimed t h a t a new m e t h o d in this respect has been developed in this s t u d y .
T h e r e f o r e , it can be concluded t h a t the s p e c t r o p h o t o m e t r i c m e t h o d can be used to measure the COD of
s e a w a t e r w i t h satisfactory results.

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