An Improved Method For Determination of Corrosion Inhibitirs in Engine Coolants

Application
Note: 204
An Improved Method for Determination

of Corrosion Inhibitors in Engine Coolants
Xu Qun and Li Lang
Introduction
Engine Coolants
Corrosion
Inhibitors
Mixed-Mode
Aqueous solutions of ethylene glycol are widely used as

engine coolants or antifreeze agents in internal combustion
engines. The freezing point of engine coolant formulations
is affected by changes in the percentage of ethylene
glycol in the product. Corrosion inhibitors are added to
coolant soutions because glycolic acid (generated from
the oxidation of ethylene glycol at 80110 C) can erode
cooling systems, especially if copper ions are present.
(Radiator temperatures regularly reach over 110 C
when an automobile is running.) No single inhibitor can
protect against all corrosive agents; therefore, multiple
inhibitors are typically added to antifreeze formulations.
The most commonly used inhibitors are azole compounds
(e.g., benzotriazole [BT], tolyl-triazole [TT], and
2-mercaptobenzothiazole [MBT], organic acids (e.g.,
sebacic acid, 2-ethyl hexanoic acid, and benzoic acid), and
inorganic salts (e.g., silicates, borates, and phosphates).
Several publications report determination of inhibitor
components in antifreeze solutions and their ability to
protect against corrosion; Schmitt et al.1 reported an
HPLC method for determination of MBT, TT, and BT
in ethylene glycol-based engine coolants. The authors
used an isocratic eluent system of methanol/aqueous
sodium acetate buffer in conjunction with a C18 column.
Beckwith et al.2 determined 14 major and trace elements
in antifreeze solutions using inductively coupled plasma
atomic emission spectrometry (ICP-AES) to evaluate the
ability of these solutions to protect against corrosion.
Reversed-phase chromatography of MBT and BT was
shown in a study of the effect of ozonation on MBT in
water and tannery wastewater.3
The methods mentioned above have limitations regarding
selectivity, and require time-consuming sample preparation
and analysis. The following describes a method for improved
determination of corrosion inhibitors in antifreeze solutions using
the Thermo Scientific Acclaim Mixed-Mode WAX-1 column.
This column incorporates a mixed-mode bonded phasea
silica-based packing material covalently functionalized with
a silyl ligand that incorporates both hydrophobic and weak
anion-exchange properties.4 Unlike traditional reversedphase stationary phases in which the silica is modified with
a long alkyl chain, the Acclaim Mixed-Mode WAX-1
column features a long alkyl chain with an ionizable tertiary
amine terminus.
Here, the authors report an HPLC method that uses

the Acclaim Mixed-Mode WAX-1 column to determine
glycolic acid and six corrosion inhibitors, including
BT, TT, MBT, sebacic acid, 2-ethyl hexanoic acid, and
benzoic acid (structures shown in Figure 1) in a single
injection. The effect of different concentrations and pH
values of the buffer in the mobile phase are examined.
Following method optimization, the authors determine the
concentrations of corrosion inhibitors in seven commercial
engine coolants.
N
N
N
CH3
N
SH
H3 C
OH
H 3C
Tolyl-triazole 2-Mercaptobenzothiazole
2-Ethyl-hexanoic acid
O
HO
OH
O
Sebacic acid
O
N
N
N
H
1H-Benzotriazole
OH
HO
Benzoic acid
CH2OH
Glycolic acid
25496
Figure 1: Structures of seven antifreeze additives used as corrosion inhibitors.
Equipment
Thermo Scientific Dionex UltiMate 3000 HPLC system:
HPG 3400A Pump with SRD 3400 Solvent Rack
with degasser
TCC-3000 Thermostatted Column Compartment
WPS-3000TSL Autosampler
VWD-3400 Variable Wavelength Detector
Thermo Scientific Dionex Chromeleon 6.80 SP3
Chromatography Data System (CDS) software
Note: This method requires a pump that mixes at high pressure.
Reagents and Standards
Gradient:
Deionized water, (Milli-Q ) Gradient A10
Acetonitrile (CH3CN), HPLC grade (Cat.#AC610010040)

Fisher Chemical
7.0
35
65
9.0
35
65
Tolyl-triazole, 99.5%, Dr. Ehrenstorfer, USA
9.5
70
30
2-Mercaptobenzothiazole, 98%, Acoros, USA
15.0
70
30
Sebacic acid disodium salt, TCI, Tokyo, Japan
Flow Rate:
1.0 mL/min
2-Ethyl hexanoic acid, 99.0%, Dr. Ehrenstorfer, USA
Inj. Volume:
10 L
Glycolate, 99%, Chem Service, PA, USA
Detection:

Absorbance at 214 nm, 220 nm,

260 nm, and 320 nm
1H-Benzotriazole, 90%, Acoros, USA

Sodium benzoate, SCRC, China
Samples
Seven antifreeze samples from different manufacturers
were tested. Samples were purchased locally.
Mobile Phase A Preparation

Prepare 100 mM KH2PO4 by dissolving 13.6 in 800 mL
of deionized water. Transfer to a 1 L volumetric flask and
bring to volume. Prepare 100 mM H3PO4 by adding
1.44 mL H3PO4 to a 250-mL volumetric flask, dilute to the
mark with H2O. The mobile is prepared by mixing 700 mL
of 100 mM KH2PO4 with 100 mL 100 mM H3PO4.
Conditions
Acclaim Mixed-Mode WAX-1 column,
5 m, 4.6 150 mm (P/N: 064984)
Column Temp.: 30 C
B. CH3CN
Analyte
The concentrations of stock standard solutions were

200 mg/L for MBT, 1,000 mg/L for TT, benzoate, and BT,
4,000 mg/L for sebacate, and 10,000 mg/L for glycolate
and 2-ethyl hexanoate. Standards were prepared in water.
Mixed Working Standard Solutions

Five mixed working standard solutions used for calibration
were prepared by making serial dilutions of the stock
standard solutions. The compositions of the mixed
working standard solutions are shown in Table 1.
Sample Preparation
For samples 14, pipet 2.5 mL of each sample into a
10 mL volumetric flask and bring to volume with
deionized water. For samples 57, pipet 2.5 mL of each
sample into a 25 mL volumetric flask and bring to volume
with water. Filter the dilutions though a 0.45 m filter
prior to injection.
BT
Glycolate
TT
10,000
1,000
12.5
10
1,000
Benzoate
Mixed working standard 1

Sebacate
MBT
2-Ethyl Hexanoate
4,000
200
10,000
1,000
1.00 mL
Volume of mixed working standard

Vol. of added stock standard (L)
30
When analyzing an engine coolant for the first time, the

authors suggest beginning with dilutions of 1:5 and 1:10
to prevent column overload and empirically determine the
appropriate dilution.
Mobile Phase: A. 100 mM KH2PO4-H3PO4 buffer

(pH 3.07)
Concentration of stock standard (mg/L)
70
Stock Standard Solutions
Potassium dihydrogen phosphate, analytical grade,

SCRC, China
0.0
Preparation of Standards and Samples
Phosphoric acid, analytical grade, SCRC, China
Column:

Time (min) A (%) B (%) Curve
3.75
Concentration (mg/L)
12.5
100
3.75
25
20
10
7.5
25
200
10
7.5
50
40
20
50
400
20
31.25
125
25
37.5
375
50
75
250
10
750
15
125
100
150
15
500
20
1500
62.5
100
80
40
30
187.5
200
200
100
800
40
30
750
40
2000
120
90
50
45
235
240
220
120
900
50
45
940
48
2200
Table 1: Concentrations of mixed working standard solutions.
Results and Discussion
Influence of the Mobile Phase Buffer on Retention
Separations of Corrosion Inhibitors and Glycolic Acid on

Different Acclaim Columns
The authors evaluated the effect of the phosphate buffers

pH, concentration, and proportion in the mobile phase on
separation of engine coolant analytes using the Acclaim
Mixed-Mode WAX-1 column. In these studies, the five
compounds in Figure 2 were evaluated along with MBT.
The buffer pH was adjusted by changing the proportion
of phosphoric acid and potassium dihydrogen phosphate.
As shown in Figure 3, the retention times of glycolate and
2-ethyl hexanoate increased slightly, those of sebacate and
benzoate increased significantly as pH buffer concentration
increased, while TT and MBT exhibited stable retention
behaviors when buffer pH value changed. Good separation
was obtained at pH < 3.25; glycolate, however, was poorly
retained at pH values < 3, therefore a pH value of 3.07
was chosen.
The main component in antifreeze is glycol, and its

percentage in antifreeze formulations is typically >50%.
Antifreeze should not contain glycolic acid, which can
damage automobile engines. Glycolic acid is created in
antifreeze from the oxidation of glycol, especially when Cu2+
is present. Glycolic acid (Figure 1) is highly polar, and typical
reversed-phase silica columns such as the Acclaim 120 C18
and those designed to work with aqueous mobile phases to
allow retention of some polar analytes (e.g., Acclaim PA and
PA2 columns) are unable to provide adequate retention of
glycolic acid (peak 1, Figure 2).
Additionally TT (peak 2, Figure 2) coelutes with sebacate
(peak 3, Figure 2); and MBT (peak 4, Figure 2) coelutes
with 2-ethyl hexanoate (peak 5, Figure 2) using the
PA column (chromatogram). The PA2 column also
demonstrates unsatisfactory resolution between TT and
sebacate. Although all compounds are resolved using the
120 C18, the retention of glycolic acid is poor (k = 0.21).
The Acclaim Mixed-Mode WAX-1 column resolves all five
compounds and demonstrates good retention of glycolic
acid (k = 0.83), making it the best choice for the analysis of
engine coolants.
A:
B:
C:
D:
Acclaim C18 (4.6 150 mm)

Acclaim PA (4.6 150 mm)
Acclaim PA2 (4.6 150 mm)
Acclaim Mixed-Mode WAX-1
(4.6 150 mm)
Eluents:
Columns A-C
A: 0.5% H3PO4 in water
B: Acetonitrile gradient
Column D
A: 100 mM KH2PO4 - H3PO4 buffer
B: Acetonitrile, isocratic (A-42%, B-58%)
Temperature: 30 C
Flow Rate: 1.0 mL/min
Inj. Volume: 5 L
Detection: UV at 210 nm
Sample:
Mixture of 5 compounds
Peaks:
1
D
3
2
2,3
140
3
4
Minutes
5
5
TT
10
benzoate
sebacate
MBT
2-ethyl hexanoate
2.16 2.87
3.25 3.77 4.12

pH value
25483
Figure 4 shows the effect of buffer concentration

on retention time. The retention time of TT remained
stable, while the retention times of other compounds
decreased as the buffer concentration increased. At
25 mM, MBT, sebacate, and benzoate began to coelute.
The best separation of the six compounds was achieved
using 100 mM buffer.
12
Figure 3: Effect of pH value of phosphate buffer on retention time.
4,5
glycolate
B
1
14
mAU C
16
1. Glycolate
2. Tolyl-triazole (TT)
3. Sebacate
4. 2-Mercaptobenzothiazole (MBT)
5. 2-Ethyl hexanoate
120
Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

A: 100 mM KH2PO4 H3PO4 buffer with different
pH values
Temperature: 30 C
Inj. Volume: 10 L
Retention time
(min)
Column:
Column:
Eluent:
7.5
25482
Figure 2: Chromatograms of the corrosion inhibitors and glycolate using

different Acclaim columns.
Column:
Eluent:

A: KH2PO4 H3PO4 buffer (pH 3.25) with
different concentrations
Temperature: 30 C
Inj. Volume: 10 L
glycolate
TT
benzoate
sebacate
MBT
2-ethyl hexanoate
10
Retention time
(min)
25
50
75
100
Buffer concentration (mM)
25484
Figure 4: Effect of phosphate buffer concentration on retention time.
Figure 5 shows the influence on retention time of the buffer

proportion in the mobile phase. The retention time of
glycolate remained stable, while the retention times of other
compounds increased with an increase in buffer proportion
(the percentage of organic solvent in the mobile phase
decreased at the same time; in this experiment, organic
solvent has the greatest influence on retention). Satisfactory
resolution of the six compounds was observed when the
buffer proportion in the mobile phase was between 6065%.
Experiments that examine the influence of the buffer

concentration in the mobile phase show the differences
between the Acclaim Mixed Mode WAX column and
typical reversed-phase columns. From the retention time
changes demonstrated by changing the buffer pH value or
concentration, the anion-exchange properties of the column
can be observed, while the influence of the buffer proportion
relative to the organic solvent portion of the mobile phase
demonstrates the reversed-phase properties of the column.
Figures 26 demonstrate that glycolate has little or no
retention on a reversed-phase column, and its retention
on the Acclaim Mixed-Mode WAX-1 column is due to its
anion-exchange properties.
In addition to the six compounds investigated above,
1H-benzotriazol (BT, Figure 1), a compound with high
polarity, is often used as a corrosion inhibitor in antifreeze.
Figure 6 shows chromatograms of BT and glycolate with
a varying proportion of phosphate buffer (pH 3.07) in
the mobile phase. The retention time of BT changed
significantly while glycolate remained unchanged
when the buffer proportion was increased from 57% to
63%. This demonstrates the tunable selectivity of the
Acclaim Mixed-Mode WAX-1 column. A change in the
percentage of organic solvent has no effect on glycolate
retention, but does affect the retention of BT that is
governed by the reversed-phase property of the column.
Because small changes in the proportion of buffer can
influence this separation, the use of gradient elution may
be beneficial for separating glycolate and BT in the same
injection as the other five compounds of interest.
Column:
Acclaim Mixed-Mode WAX-1

(4.6 150 mm)
Eluent:
A: 100 mM KH2PO4 H3PO4 buffer
(pH 3.07) with different proportions
B: Acetonitrile, isocratic
Flow Rate:
1.0 mL/min
Temperature:
30 C
Inj. Volume:
10 L
Detection:
UV at 214 nm
Chromatograms: A: 57% eluent A
B: 60% eluent A
C: 63% eluent A
Column:
Eluent:

A: KH2PO4 H3PO4 buffer (pH 3.25) with
different proportion in eluent
B: Acetonitrile, isocratic
Temperature: 30 C
Inj. Volume: 10 L
Peaks:
16
300 A
14
glycolate
12
TT
10
Retention time
(min)
1. Glycolate
2. Benzotriazole (BT)
mAU
50
250 B
benzoate
MBT
2-ethyl hexanoate
mAU
20
50 55 60 65 70
Buffer Proportion (%)
Figure 5: Effect of phosphate buffer proportion in the mobile phase.
25485
50
220 C
2
45
mAU
sebacate
1,2
2
1
2.2
2.4
2.6
2.8
Minutes
3.2
3.5
25486
Figure 6: Chromatography of glycolate and BT using different proportions of

phosphate buffer in the mobile phase.
Figure 7 shows separation using gradient elution, and

demonstrates good resolution between glycolate, BT, and
all seven compounds.
Column:
Eluent:

A: 100 mM KH2PO4 H3PO4 buffer (pH 3.07)
Temperature: 30 C
Inj. Volume: 10 L
Detection:
UV at 220 nm

A: 100 mM KH2PO4 H3PO4 (pH 3.07)
Flow Rate:
1.0 mL/min
Temperature:
30 C
Inj. Volume:
10 L
Detection:
UV at 214, 220, 260 and 320 nm
Sample:
100 g/L mixture of standards
Chromatograms: A: Detected at 214 nm
B: Detected at 220 nm
C: Detected at 260 nm
D: Detected at 320 nm
Peaks:
Peaks:
Column:
Eluent:
1. Glycolate
4. Benzoate
5. Sebacate
6. 2-Mercaptobenzothiazole
(MBT)
4
150
mAU
65%
6
mAU
5
1
1.3
2.5
3.8
5
Minutes
6.3
7.5
8.8
10
25487
Figure 7: Separation of seven engine coolant analytes using an

acetonitrile gradient.
UV-vis Spectrum of Glycolate and Inhibitors

Analysis of UV-vis spectra between 190 and 500 nm
show that glycolate, TT, sebacate, and 2-ethyl hexanoate
demonstrate good absorbance at 214 nm; benzoate at
220 nm, BT at 260 nm, and MBT at 320 nm. Figure 8
shows chromatograms of a mixture of standards observed
at different absorbance wavelengths. The authors used all
four wavelengths for sample analysis.
Reproducibility, Linearity and Detection Limits

Prior to sample analysis, the authors studied method
reproducibility by making five replicate injections of an
antifreeze sample spiked with a mixed standard solution.
The relative standard deviations (RSDs) for retention time
and peak area are shown in Table 2.
Analyte
Retention Time RSD
Peak Area RSD
Glycolate
0.390
0.553
BT
0.101
0.317
TT
0.096
0.335
Benzoate
0.000
0.194
Sebacate
0.000
2.15
MBT
0.066
0.286
2-Ethyl hexanoate
0.060
3.165
Table 2: Results of reproducibility experiments.
50
350 B
%B: 30%
2
500 A
10
1. Glycolate
4. Benzoate
5. Sebacate
5
6
4
2
mAU
50
800 C
mAU
100
800 D
6
6
mAU
100
Minutes
10
25488
Figure 8: Chromatograms of seven engine coolant analytes using different

detection wavelengths.
Calibration linearity for the compounds was investigated

by making seven replicate injections of a mixed standard
solution prepared at five different concentrations. The
external standard method was used to calculate the
calibration curve and to quantify these compounds in the
samples. Table 3 reports the data from the calibration as
calculated by Chromeleon CDS software. The singlesided Students-t test method was used to estimate method
detection limits (MDL). These data are also reported in
Table 4.
Analyte
Equation
RSD
MDL
(mg/L)
Glycolate
A = 0.0024 c + 0.0093
99.9760
1.0526
0.88
BT
A = 0.1147 c - 0.0213
99.9872
0.8377
0.64
TT
A = 0.2082 c + 0.0992
99.9290
1.9252
0.10
Benzoate
A = 0.6311 c - 0.3690
99.8992
2.5381
3.40
Sebacate
A = 0.0025 c - 0.0009
99.9223
1.6602
2.75
MBT
A = 0.6644 c - 0.0749
99.9802
0.9669
1.05
2-Ethyl hexanoate
A = 0.0080 c - 0.0693
98.4407
7.5663
5.43
Note: The single-sided Student's-t test method (at 99% confidence limit) was used to determine
MDL, where the standard deviation (SD) of the peak area of seven injections is multiplied by 3.14
to yield the MDL.
Table 3: Calibration data and MDLs for the seven analytes (as reported by
Chromeleon CDS software).
Column:
Eluent:

Flow Rate:
1.0 mL/min
Temperature:
30 C
Inj. Volume:
10 L
Detection:
UV at 214, 220, 260 and 320 nm
Sample:
Chromatograms: A: Sample 4 spiked with mixture standards
B: Sample 4 (eightfold dilution)
C: Blank (H2O)
D: Ethylene glycol (50%, with H2O)
Conc. of spiked mixture
standards (g/mL)
1. Glycolate
230
25
10
4. Benzoate
5
5. Sebacate
125
5
750
Peaks:
Sample Analysis
Seven antifreeze samples were analyzed; sample
chromatograms are shown in Figures 9 and 10. Figure 9
shows chromatograms of sample 4, along with the same
sample spiked with standards. Figure 10 shows overlay
chromatograms of the remaining six samples. Analysis
results, i.e., amounts of the corrosion inhibitors in each
sample, are summarized in Table 4. Glycolate was not
detected in any of the samples. BT, sebacate, and benzoate
were found in samples 5 and 6; TT and 2-ethyl hexanoate
were found in samples 1 through 4. Sample 7 contained
only minimal amounts of inhibitor. Samples 1 through 6
contained unidentified peaks. Samples 1 though 4 each
exhibited a peak at approximately 9.8 min, and samples 2
and 3 both exhibited a small peak eluting at approximately
7.9 min, after 2-ethyl hexanoate. It is possible this peak is
the same as that observed in samples 5 and 6.
1,400
A: 214 nm
mAU
1
A
B
C
D
600
400
4 56
25489
B: 220 nm
mAU
1
A
B
C
D
Conclusion
The Acclaim Mixed-Mode WAX-1 column provides
the most effective HPLC solution for analyzing
corrosion inhibitors in engine coolants. All seven
compounds, including six corrosion inhibitors and a
possible contaminant (glycolic acid), are well resolved
and demonstrate good peak efficiency and asymmetry
within a 10-min run time. This separation can be used
for quality control of engine coolants or for testing the
effect of different driving or environmental conditions
on stability and/or effectiveness of an engine coolant.
Unlike previously developed methods for determination
of these compounds, this method requires no sample
preparation other than simple dilution and filtration, and
provides improved selectivity and sensitivity of the target
compounds in this complex matrix.
150
4 6
5
800
C: 260 nm
mAU
A
B
C
D
300
100
25490
4 6
25491
D: 320 nm
mAU
40
A
B
C
D
0
Minutes
11
25492
Figure 9: Chromatograms of Sample 4. Trace A: Sample diluted eightfold,

spiked with mixed standards. Trace B: Sample diluted eightfold. Trace C:
System blank. Trace D: Ethylene glycol diluted 1:1 with DI H2O. All
samples were analyzed with data collected using four different wavelengths;
chromatogram A: 214 nm, B: 220 nm, C: 260 nm, D: 320 nm.
Sample1
Sample 2
Sample 3
Detected
(g/mL)
Detected
(g/mL)
Detected
(g/mL)
Detected
(g/mL)
Added
(g/mL)
Glycolate
ND
ND
ND
ND
230
BT
ND
ND
ND
ND
25
TT
1,212
1,200
1,356
1,320
10
Benzoate
ND
ND
ND
Sebacate
ND
ND
ND
ND
125
MBT
ND
ND
ND
ND
10,440
99,608
112,992
102,400
Analyte
2-Ethyl hexanoate
Sample 4
21
Notes:
1. Three injections were made for each sample
2. Detected = Measured value of sample multiplied by dilution factor
3. Found = Measured value of spiked sample minus measured value of sample
4. ND = Not Detected
5.0
1,500
Sample 5
Sample 6
Sample 7
Recovery
(%)
Detected
(g/mL)
Detected
(g/mL)
Detected
(g/mL)
102
ND
ND
ND
27.3
109
255
172
ND
9.9
99
ND
ND
ND
4.55
91
3,856
4,030
7.0
109
2,170
2,453
ND
118
ND
ND
ND
103
ND
ND
ND
Found
(g/mL)
234
136
5.91
1,543
References

Flow Rate:
1.0 mL/min
Temperature:
30 C
Inj. Volume:
10 L
Detection:
UV at 220 nm
Sample:
Chromatograms: A: Sample 1 (fourfold dilution)
B: Sample 2 (fourfold dilution)
C: Sample 3 (fourfold dilution)
D: Sample 5 (tenfold dilution)
E: Sample 6 (tenfold dilution)
F: Sample 7 (tenfold dilution)
1. Schmitt, Thomas M.; and Muzher, Ead S. Determination of

2-mercaptobenzothiazole, tolyltriazole and benzotriazole in coolant
formulations by liquid chromatography. Talanta 1981, 28, 777779.
2. Beckwith, Paul M. Determination of major and trace elements in glycolbased fluids by inductively coupled plasma atomic emission spectrometry.
Spectrochimica Acta (B): Atomic Spectroscopy 1985, 40, 301306.
3. Fiehn, O.; Wegener, G.; Jochimsen, J.; and Jekel, M. Analysis of the
ozonation of 2-mercaptobenzothiazole in water and tannery wastewater
using sum parameters, liquid- and gas chromatography and capillary
electrophoresis. Water Research 1998, 32, 10751084.
4. User Guide for Acclaim Mixed-Mode WAX Columns, Dionex
Corporation. Doc. # 065165
4. Benzoate
5. Sebacate
4
F
E
D
mAU
5
7
C
B
A
0
Minutes
Scientific maintains
a network of represen
tative organizations
throughout the world.
North America:
U.S./Canada
(847) 295-7500
Column:
Eluent:
offices, Thermo Fisher
Dionex Products:
(408) 737-0700
Table 4: Analysis results for engine coolant products.
Peaks:
In addition to these
11
25493
South America:
Brazil
(55) 11 3731 5140
Europe:
Austria
(43) 616 51 25
Benelux
(31) 20 683 9768
(32) 3 353 4294
Denmark
(45) 36 36 90 90
France
(33) 1 39 30 01 10
Germany
(49) 61125 991 0
Ireland
(353) 644 0064
Italy
(39) 02 51 62 1267
Sweden
(46) 8 473 3380
Switzerland
(41) 62 205 9966
United Kingdom
(44) 1276 691722
Asia Pacific:
Australia
(61) 2 9420 5233
China
(852) 2428 3282
India
(91) 22 2764 2735
Japan
(81) 6885 1213
Korea
(82) 2 2653 2580
Singapore
(65) 6289 1190
Taiwan
(886) 2 875 6655
Figure 10: Chromatograms of samples 13 and 57.
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An Improved Method For Determination of Corrosion Inhibitirs in Engine Coolants

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An Improved Method for Determination

Aqueous solutions of ethylene glycol are widely used as

Here, the authors report an HPLC method that uses

Figure 1: Structures of seven antifreeze additives used as corrosion inhibitors.

Reagents and Standards

Deionized water, (Milli-Q ) Gradient A10

Acetonitrile (CH3CN), HPLC grade (Cat.#AC610010040)

Tolyl-triazole, 99.5%, Dr. Ehrenstorfer, USA

2-Mercaptobenzothiazole, 98%, Acoros, USA

Sebacic acid disodium salt, TCI, Tokyo, Japan

2-Ethyl hexanoic acid, 99.0%, Dr. Ehrenstorfer, USA

Glycolate, 99%, Chem Service, PA, USA

Absorbance at 214 nm, 220 nm,

1H-Benzotriazole, 90%, Acoros, USA

Mobile Phase A Preparation

The concentrations of stock standard solutions were

Mixed Working Standard Solutions

Mixed working standard 1

Volume of mixed working standard

When analyzing an engine coolant for the first time, the

Mobile Phase: A. 100 mM KH2PO4-H3PO4 buffer

Concentration of stock standard (mg/L)

Stock Standard Solutions

Potassium dihydrogen phosphate, analytical grade,

Preparation of Standards and Samples

Phosphoric acid, analytical grade, SCRC, China

Time (min) A (%) B (%) Curve

Vol. of added stock standard (L)

Vol. of added stock standard (L)

Vol. of added stock standard (L)

Vol. of added stock standard (L)

Table 1: Concentrations of mixed working standard solutions.

Results and Discussion

Influence of the Mobile Phase Buffer on Retention

Separations of Corrosion Inhibitors and Glycolic Acid on

The authors evaluated the effect of the phosphate buffers

The main component in antifreeze is glycol, and its

Acclaim C18 (4.6 150 mm)

3.25 3.77 4.12

Figure 4 shows the effect of buffer concentration

Figure 3: Effect of pH value of phosphate buffer on retention time.

Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

Figure 2: Chromatograms of the corrosion inhibitors and glycolate using

Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

Buffer concentration (mM)

Figure 4: Effect of phosphate buffer concentration on retention time.

Figure 5 shows the influence on retention time of the buffer

Experiments that examine the influence of the buffer

Acclaim Mixed-Mode WAX-1

Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

Figure 5: Effect of phosphate buffer proportion in the mobile phase.

Figure 6: Chromatography of glycolate and BT using different proportions of

Figure 7 shows separation using gradient elution, and

Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

Acclaim Mixed-Mode WAX-1 (4.6 150 mm)

Figure 7: Separation of seven engine coolant analytes using an

UV-vis Spectrum of Glycolate and Inhibitors

Reproducibility, Linearity and Detection Limits

Retention Time RSD

Peak Area RSD

Table 2: Results of reproducibility experiments.

Figure 8: Chromatograms of seven engine coolant analytes using different