Conductometric determination of

sulfuric acid in battery fluid

Edwin J. Alvarado-Rodrguez
Freddy A. Rodrguez-Ortiz
Contents

1 Introduction 3

2 Data & Results 4

2.1 Standardization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3 Discussion & Conclusion 11

4 References 12

5 Appendix 13
5.1 Carbon copies from laboratory journals of EJAR & FARO which include
original data, material safety information, and protocol reference. . . . . 13
5.2 Manufacturer MSDS reporting analyte amount . . . . . . . . . . . . . . 23

2
1 Introduction

In the present work, we determined the sulfuric acid concentration in battery fluid by
conductometric titration against sodium hydroxide (NaOH). Conductometry is a com-
mon technique that measure the electrolytic conductivity to monitor the progress of a
chemical reaction 1 . Specifically, and for our interest in this work, in a conductomet-
ric titration, the conductance of a reaction is constantly monitored as one reactant is
added. The increase or decrease in conductance in the reaction are associated with
the changing concentrations of the two most highly conducting ions (hydrogen and
hydroxide ions), where the equivalence point may be located graphically by plotting
the change in conductance as a function of the volume of added. Herein, we have
employed a conductometric titration method to neutralize sulfuric acid in battery fluid.
Here, as the titration progresses, the protons are neutralized to form water by the ad-
dition of NaOH and the mobile hydrogen ions are replaced by the less-mobile sodium
ions, resulting in a conduction decrease of the titrated solution. At first, the conduc-
tance is low due to the feeble second ionization of sulfuric acid. But increasing the
NaOH volume in the solution, the conductance increases as NaOH neutralizes sulfuric
acid into sodium sulfate, which is a strong electrolyte. This increase in conductance
continues to the equivalence point. Beyond the equivalence point, conductance in-
creases more rapidly with the addition of NaOH due to the highly conductive OH- ions.
Through this experiment, we have taken measurements with the conductometer; and
further determined the amount of sulfuric acid in battery fluid, reported by the manu-
facturer as 4.534 mol L1 .

3
2 Data & Results

2.1 Standardization
To determine the concentration of sulfuric acid in battery fluid, we performed a con-
ductometric titration with NaOH. All conductometric measurements were performed in
a CORNING Pinnacle 541 conductivity meter.
Firstly, we standardize a solution of sodium hydroxide against potassium hydrogen
phthalate, KHP. Three samples of KHP were weighed and titrated with NaOH while
measuring conductance as a function of NaOH volume. Ammonium hydroxide was
added to aid in KHP ionization. Sample mass and conductometric titration can be
found in Table 2.1. Plots of the conductometric titration can be found in Figure 2.1. The
curve has two linear regimes, which were fitted into their own individual least-squares
regressions. The regression parameters can be found in Table 2.2.

450
Conductance / (S cm1)

400

350

300

1
2
250 3

0.00 3.00 6.00 9.00 12.00 15.00 18.00

Titrant / (mL)

Figure 2.1: Conductance versus titrant volume plots of the conductometric titration
curves for standard KHP. Regression curves plotted foreach titration, where
the left and right fits are regressions 1 and 2, respectively.

4
Table 2.1: KHP (99.5%) sample mass with corresponding NaOH conductometric
titration.

ms1 = 0.0422g ms2 = 0.0413g ms3 = 0.0397g

Volume Cond. Volume Cond. Volume Cond.

(mL) (S cm1 ) (mL) (S cm1 ) (mL) (S cm1 )
0.00 405 0.00 322 1.11 357
0.52 404 0.98 319 2.00 353
0.99 401 2.01 315 3.00 350
2.01 396 3.00 313 4.10 347
3.11 391 4.61 308 4.99 343
4.01 388 5.00 307 6.01 340
5.00 382 6.01 306 7.00 338
6.00 378 7.01 304 8.01 337
7.01 375 8.01 303 9.01 335
7.99 372 9.01 302 10.00 336
9.05 370 10.00 303 11.00 337
10.00 369 11.00 305 12.00 339
10.99 368 11.99 307 13.00 344
12.00 370 13.00 312 14.02 351
12.98 371 14.00 318 15.01 359
13.99 375
15.00 380
16.00 388
17.00 398
18.01 409

5
Table 2.2: Regression parameters of the left (1) and right (2) least-squares interpola-
tion of the standard titration (m are slopes, b are intercepts, R 2 are correla-
tion coefficients.) Values in parentheses are the standard deviations of their
corresponding parameters.
Standard m1 b1 R12 m2 b2 R22
# (S cm1 mL1 ) (S cm1 ) (S cm1 mL1 ) (S cm1 )
1 -3.89 (0.18) 403 (1) 0.98 10.4 (0.3) 220 (4) 1.00
2 -2.43 (0.16) 320 (1) 0.97 5.47 (0.30) 241 (3) 1.00
3 -2.99 (0.18) 359 (1) 0.98 7.46 (0.35) 247 (5) 1.00

The volume of equivalence of the titration can be found by the intersection of the two
regressions. Therefore, it can be calculated by equation 2.1.

b2 b1
Veq = (2.1)
m1 m2
An example calculation can be seen below. Results are included in Table 2.3.

220 S cm1 403 S cm1

Veq =
3.89 S cm1 mL1 10.4 S cm1 mL1

Table 2.3: Equivalence volumes for the conductometric titration of each standard. Val-
ues in parentheses represent standard deviation of the respective volume.
Standard Volume, Veq
# (mL)
1 12.79 (1.36)
2 10.06 (1.42)
3 10.75 (1.42)

These volumes were used to calculate the concentration of the NaOH standard
solution using equation 2.2.

1
0.995 ms MMKHP
CNaOH = (2.2)
Veq
where ms is the standard mass of the corresponding titration, MMKHP is the molar mass
of KHP, and Veq is the equivalence volume in Liters. An example calculation can be
seen below. Concentrations are summarized in Table 2.4.

(0.995)(0.0422g )(204.22g mol 1 )

CNaOH =
0.01279L

6
Table 2.4: Concentrations as calculated from the conductometric titration of each stan-
dard.Values in parentheses are the propagated errors.
Standard Concentration
# (mol L1 )
1 0.0161 (0.0017)
2 0.0200 (0.0028)
3 0.0180 (0.0024)

The standardized concentration of NaOH was determined to be the inverse-variance

weighted mean of the determined concentrations in order to reduce the effects of the
less precise determinations,

CNaOH = 0.0174 mol L1

2.2 Determination
A 1 in 100 dilution of battery fluid was prepared for sulfuric acid determination. 1 mL
of this solution was titrated with the standardized sodium hydroxide in triplicate. Con-
ductometric titrations can be found in Table 2.5. Plots of the conductometric titration
can be found in Figure 2.2.
The sample was analyzed the same way as the standard. Regression parameters
for the analysis of each sample are in Table 2.6. Equivalence volumes can be found in
Table 2.7.
The H2 SO4 concentration was calculated using equation 2.3.

Veq CNaOH 1 molH2 SO4

CH2 SO4 = D (2.3)
Vs 2 molNaOH
where V is in Liters and D is the dilution factor. An example calculation can be found
below.

(0.00598L) (0.0174 mol L1 ) 1 molH2 SO4 1.000mL

CH2 SO4 =
0.001L 2 molNaOH 100.00mL
Sulfuric acid content is tabulated in Table 2.8.

7
 Table 2.5:

Sample 1 Sample 2 Sample 3

Volume Cond. Volume Cond. Volume Cond.

(mL) (S cm1 ) (mL) (S cm1 ) (mL) (S cm1 )
0.00 323.00 0.00 335.0 0.00 251
0.56 299 1.00 293.0 1.02 216
1.55 259 2.02 249.0 2.00 186
2.55 219 3.01 207.0 2.99 156.5
3.55 181 4.12 164.8 4.00 125.6
4.55 143.8 5.00 132.3 5.00 95.7
5.55 107.1 6.00 96.0 5.99 73.2
6.55 101.1 7.00 111.6 7.01 89.1
7.55 125.7 8.36 149.0 8.10 111.2
8.55 153.4 9.00 166.3 9.06 131.4
10.53 203 10.00 192 10.02 152.0
11.55 228 11.00 218 11.00 171.1
12.56 253 12.01 242 12.00 191
13.56 277 12.99 266 13.00 210
14.55 299 14.00 290 14.02 229
15.00 312

8
 350

Conductance / (S cm1) 300

250

200

150.0

100.0

50.0
1
2
0.0 3

0.00 3.00 6.00 9.00 12.00 15.00

Titrant / (mL)

Figure 2.2: Conductance versus titrant volume plots of the conductometric titration
curves for battery fluid plotted for each titration, where the left and right
fits are regressions 1 and 2, respectively.

Table 2.6: Regression parameters of the left (1) and right (2) least-squares interpo-
lation of the battery fluid titration (m are slopes, b are intercepts, R 2 are
correlation coefficients.) Values in parentheses are the standard deviations
of their corresponding parameters.
Sample m1 b1 R12 m2 b2 R22
# (S cm1 mL1 ) (S cm1 ) (S cm1 mL1 ) (S cm1 )
1 -38.9 (0.4) 320 (1) 1.00 24.9 (0.2) -60.9 (2.4) 1.00
2 -40.7 (0.6) 333 (2) 1.00 24.7 (0.3) -55.8 (3.4) 1.00
3 -30.8 (0.4) 249 (1) 1.00 19.8 (0.2) -47.7 (2.1) 1.00

Table 2.7: Equivalence volumes for the conductometric titration of each sample. Val-
ues in parentheses represent standard deviation of the respective volume.
Sample Volume, Veq
# (mL)
1 5.98 (0.18)
2 5.94 (0.26)
3 5.86 (0.20)

9
Table 2.8: Sulfuric acid content in battery fluid as determined by conductometric
titration.
Sample Concentration, CH2 SO4
# (mol L1 )
1 5.19 (0.15)
2 5.16 (0.22)
3 5.08 (0.17)

2.3 Results
A summary of the statistical analysis of the results is presented in Table 2.9. The
manufacturer reports a sulfuric acid concentration of 4.534 mol L1 .

Component Concentration RSD Relative Error

1
(mol L ) (ppt) (%)
Sulfuric Acid 5.15 (0.06) 11 13

Table 2.9: Mean concentration of sulfuric acid in battery fluid. Value in parentheses is
the standard deviation.

10
3 Discussion & Conclusion

In the present study, we attempted to quantify the concentration of sulfuric acid in com-
mercial battery fluid. We chose to perform the determination of our analyte through
conductometric titration. The titrant calibration was carried out by weighing standard
KHP in triplicate and following its neutralization with NaOH using conductometry. The
equivalence volume was found by intersecting the two linear regimes of the conduc-
tometric titration. The calculated NaOH concentrations showed discrepancies, and
represent the most influential source of error in our determination. A sample of bat-
tery fluid was analyzed using the same procedure as the standard. The sulfuric acid
determinations showed excellent agreement. The accuracy was acceptable, with a
relative error of 13%. The precision of the analysis was also acceptable, with a relative
standard deviation of 11 ppt.
In conclusion, the determination of sulfuric acid in battery fluid was successful. The
analysis performance was of analytical quality in terms of precision. Discrepancies
between reported and determined values were present due to ill standardization of the
titrant.

11
4 References

1. Khopkar, S.M. Basic Concepts of Analytical Chemistry, 3rd edition, 2007, ISBN
978-81-224-2092-0

12
5 Appendix

5.1 Carbon copies from laboratory journals of EJAR &

FARO which include original data, material safety
information, and protocol reference.

13
5.2 Manufacturer MSDS reporting analyte amount

23
Colonial Chemical Company A Unit of The ESS Group, Inc.

Manufacturers of Quality Electrolyte and Blended Products.

78 Carranza Road, Tabernacle, NJ 08088 !"(609) 268-1200 ! (609) 268-2117 Fax

MATERIAL SAFETY DATA SHEET

PRODUCT: BATTERY FLUID, ACID 10% - 51%

MANUFACTURER/DISTRIBUTOR

Colonial Chemical Company Product Information: (609) 268-1200

78 Carranza Road Emergency: CMB(800) 457-4280
Tabernacle, NJ 08088

IDENTITY
Chemical Name: Battery fluid, acid; Electrolyte battery acid, Sulfuric acid
Chemical Family: Mineral Acid, Inorganic acid
Molecular Formula: H2SO4
CAS Number: 7664-93-9
Hazard Class: Corrosive Material, 8
UN/NA Number: UN 2796
WHMIS Classification: Class E - Corrosive, Class D1A
Packaging Group II
NFPA Ratings: NPCA-HMIS Ratings
Health: 3 Health: 3
Flammability: 0 Flammability: 0
Reactivity: 2 Reactivity 2
Water Reactive

EXPOSURE LIMITS
TLV (ACGIH) 1mg/m! - 8 Hr TWA STEL: 3 mg/m3
PEL (OSHA) 1 mg/m3 - 8 Hr TWA
Aquatic Toxicity: The 48 hour Tlm in flounder is 100-300 ppm.

PHYSICAL DATA
Physical State: Liquid
Appearance: Clear and odorless
Boiling Point: 10% - 210"F 51% - 270"F
Freezing Point: 10% - 25"F 51% - -30"F
Vapor Pressure: #0.3 mm Hg at 77"F
Vapor Density: 3.4
Evaporation Rate: Less than 1
Water Solubility: 100% soluble
pH: Less than 1
Battery Fluid, Acid Material Safety Data Sheet 2

COMPONENTS

Sulfuric Acid Water Specific Gravity

CAS# 7664-93-9 CAS# 7732-18-5 @ 60"F
10.77% 89.23% 1.074
20% 80% 1.145
24.85% 75.15% l.180
28.53% 71.47% l.210
30% 70% 1.222
33.33% 66.67% 1.250
35.15% 64.85% 1.265
36.99% 63.01% 1.280
38.05% 61.95% 1.290
39.25% 60.75% 1.300
41% 59% 1.315
47% 53% 1.370
50.17% 49.83% 1.401
FIRE AND EXPLOSION DATA

Flash Point: Will not burn, non-flammable

Autoignition Temperature: Not combustible
Flammability Limits in air (%) UEL: Not applicable
LEL: Not applicable
Hazards: Reacts with most metals, especially when dilute, to give flammable, potentially
explosive hydrogen gas. Follow appropriate National Fire Protection Assoc. (NFPA)
codes.
Extinguishing Media: Use media appropriate for surrounding material. Use water spray to
cool containers exposed to fire; do not get water inside containers.
Special Instructions: Evacuate personnel to a safe area. Keep personnel removed and upwind
of fire. Generates heat upon addition of water, with possible spattering. Wear full
protective clothing. Runoff from fire control may cause pollution. Neutralize runoff
with lime, soda ash, etc. Wear self-contained breathing apparatus if fumes or mists are
present.

HAZARDOUS REACTIVITY

Instability: Stable, but reacts violently with water and organic materials with evolution of
heat.
Decomposition: Releases sulfur dioxide at extremely high temperatures.
Polymerization: Polymerization will not occur.
Materials to Avoid: Vigorous reactions with water; alkaline solutions; metals, metal powder;
carbides; chlorates; fuminates; nitrates; picrates; strong oxidizing,
reducing, or combustible organic materials. Hazardous gases are evolved on contact with chemicals
such as cyanides, sulfides, and carbides.
Battery Fluid, Acid Material Safety Data Sheet 3

HEALTH HAZARD DATA

Causes severe burns to eyes, skin, and all body tissue. Eye damage may be permanent.
Destruction of tissue may result from direct chemical reaction with tissue, from thermal burns,
and from dehydration (removal of water) of the tissue.

Animal Data:
Inhalation 1 hour LC50: 347 ppm in rats
Oral LD50 2140 mg/kg in rats

The concentrated compound is corrosive to the skin and eyes of animals causing corrosion of
mucosal surfaces. Toxic effects described in animals from single exposures by inhalation
include respiratory irritation.

Exposure to the liquid by skin or eye contact may cause eye corrosion with corneal or
conjunctival ulceration; or skin burns or ulceration. Ingestion of the liquid may cause severe
burns to the mucous membranes of the mouth and esophagus. Repeated or prolonged contact
with mists may cause eye irritation with tearing or blurring of vision; or skin irritation with
discomfort or rash. Prolonged or repeated exposure may result in impaired lung function and
possible discoloration and erosion of teeth. Individuals with preexisting diseases of the lungs
may have increased susceptibility to the toxicity of excessive exposures.

CARCINOGENICITY

None of the components in this material is listed by IARC, NTP, OSHA, or ACGIH as a
carcinogen.

FIRST AID

Inhalation:
Move victim to fresh air. Give artificial respiration ONLY if breathing has
stopped. Give CPR if there is no breathing AND no pulse. Obtain medical
attention IMMEDIATELY.

Ingestion:
If swallowed, do not induce vomiting. Give large quantities of water. Call a physician.
Do not neutralize the acid. Never give anything by mouth to an unconscious person.

Skin or Eye Contact:

In case of contact, immediately (within seconds) flush eyes or skin with plenty of cold water
for at least 15 minutes while removing contaminated clothing and shoes. Call a physician.
While the patient is being transported to a medical facility apply compresses of iced water. If
medical treatment must be delayed, immerse the affected area in iced water or apply
compresses of iced water to affected areas. Do not freeze tissue.

Notes to Physician:
Battery Fluid, Acid Material Safety Data Sheet 4

Continued washing of the affected area with cold or iced water will be helpful in removing the
last traces of sulfuric acid. Creams or ointments should not be applied before or during the
washing phase of treatment.

PRECAUTIONS FOR SAFE HANDLING

Good general ventilation should be provided to keep vapor and mist concentrations be-
low the exposure limits. Have available and wear as appropriate for exposure conditions when
handling containers or operating equipment containing sulfuric acid: Chemical splash goggles;
full-length face shield/chemical splash goggle combination; acid-proof gauntlet gloves, apron,
and boots; long sleeve wool, acrylic or polyester clothing; acid proof suit and hood; and
appropriate NIOSH/MSHA respiratory protection. In case of emergency or where there is a
strong possibility of considerable exposure, wear a complete acid suit with hood, boots and
gloves. If acid vapor or mist are present and exposure limits may be exceeded, wear
appropriate NOISH/MSHA respiratory protection.

Always add acid to water - not water to acid.

SPILLS:

EPA and Superfund reportable discharge is 1000 lbs. Stop flow if possible. Use appropriate
protective equipment during clean up. Soak up small spills with dry sand, clay or
diatomaceous earth. Dike large spills, and cautiously dilute and neutralize with lime or soda
ash, and transfer to waste water treatment system. Prevent liquid from entering sewers,
waterways or low areas. Comply with Federal, State and local regulations.

WASTE:

Cleaned up material may be a RCRA Hazardous Waste on disposal. Do not flush to surface
water or sanitary sewer system. Comply with Federal, State and local regulations. If approved,
neutralize and transfer to waste treatment system.

STORAGE:

Keep out of sun and away from heat, sparks, and flame. Keep container tightly closed to
prevent leakage. Loosen closure carefully; relieve internal pressure when received and at least
weekly thereafter. Do not use pressure to empty. Do not wash out container or use it for other
purposes. Replace closure after each use.

Date: August 2, 2003

Filename: MSDS.rtf
Directory: C:\DOCUME~1\HRICAG~1.DPC\LOCALS~1\Temp
Template: C:\Documents and Settings\hricage.DPCSRV\Application
Data\Microsoft\Templates\Normal.dot
Title: MATERIAL SAFETY DATA SHEET
Subject:
Author: Linda Drury
Keywords:
Comments:
Creation Date: 3/17/1994 3:32 PM
Change Number: 22
Last Saved On: 8/4/2003 3:14 PM
Last Saved By: Linda Drury
Total Editing Time: 269 Minutes
Last Printed On: 10/21/2003 10:25 AM
As of Last Complete Printing
Number of Pages: 4
Number of Words: 1,071 (approx.)
Number of Characters: 6,107 (approx.)