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Conductometric determination of sulfuric acid in battery fluid

Edwin J. Alvarado-Rodr´ıguez Freddy A. Rodr´ıguez-Ortiz

Contents

1 Introduction

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2 Data & Results

 

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2.1 Standardization

 

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2.2 Determination .

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2.3 Results

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3 Discussion & Conclusion

 

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4 References

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5 Appendix

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5.1 Carbon copies from laboratory journals of EJAR & FARO which include original data, material safety information, and protocol

 

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5.2 Manufacturer MSDS reporting analyte amount

 

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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 L 1 .

3

Conductance / (µS cm 1 )

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 54 1 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.

450 400 350 300 1 2 250 3 0.00 3.00 6.00 9.00 12.00 15.00 18.00
450
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.

m s1 = 0.0422g

m s2 = 0.0413g

m s3 = 0.0397g

Volume

Cond.

Volume

Cond.

Volume

Cond.

(mL)

(µS cm 1 )

(mL)

(µS cm 1 )

(mL)

(µS cm 1 )

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

 

b 1

R

2

 

b 2

R

2

m 1

1

m 2

2

#

(µS cm 1 mL 1 ) (µS cm 1 )

(µS cm 1 mL 1 ) (µS cm 1 )

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.

V eq

b 2 b 1

=

m 1 m

2

(2.1)

An example calculation can be seen below. Results are included in Table 2.3.

V eq =

220 µS cm 1 403 µS cm 1

3.89 µS cm 1 mL 1 10.4 µS cm 1 mL 1

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, V eq

#

(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.

C NaOH = 0.995 m s MM

V

eq

1

KHP

(2.2)

where m s is the standard mass of the corresponding titration, MM KHP is the molar mass

of KHP, and V eq is the equivalence volume in Liters. An example calculation can be

seen below. Concentrations are summarized in Table 2.4.

C NaOH = (0.995)(0.0422g )(204.22g mol 1 )

0.01279L

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Table 2.4: Concentrations as calculated from the conductometric titration of each stan-

dard.Values in parentheses are the propagated errors.

Standard

Concentration

#

(mol L 1 )

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,

C ¯ NaOH = 0.0174 mol L 1

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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 H 2 SO 4 concentration was calculated using equation 2.3.

C H 2 SO 4 = V eq

¯

C

NaOH

V

s

1

mol H 2 SO 4

2

mol NaOH

D

(2.3)

where V is in Liters and D is the dilution factor. An example calculation can be found

below.

C H 2 SO 4 = (0.00598L) (0.0174 mol L 1 )

0.001L

1

mol H 2 SO 4

2

mol NaOH

1.000mL

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)

(µS cm 1 )

(mL)

(µS cm 1 )

(mL)

(µS cm 1 )

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

Conductance / (µS cm 1 )

350 300 250 200 150.0 100.0 50.0 1 2 0.0 3 0.00 3.00 6.00 9.00
350
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

 

b 1

R

2

 

b 2 (µS cm 1 )

R

2

m 1

1

m 2 (µS cm 1 mL 1 )

2

#

(µS cm 1 mL 1 )

(µS cm 1 )

 

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, V eq

#

(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, C H 2 SO 4

#

(mol L 1 )

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 L 1 .

Component

Concentration (mol L 1 )

RSD

Relative Error

(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

Manufacturers of Quality Electrolyte and Blended Products.

A Unit of The ESS Group, Inc.

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

MATERIAL SAFETY DATA SHEET

PRODUCT:

BATTERY FLUID, ACID

MANUFACTURER/DISTRIBUTOR

Colonial Chemical Company 78 Carranza Road

Tabernacle, NJ

08088

10% - 51%

Product Information: (609) 268-1200

Emergency:

CMB(800) 457-4280

IDENTITY Chemical Name: Battery fluid, acid; Electrolyte battery acid, Sulfuric acid Chemical Family: Mineral Acid, Inorganic acid Molecular Formula: H 2 SO 4 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) PEL (OSHA)

1mg/m ! - 8 Hr TWA 1 mg/m 3 - 8 Hr TWA

STEL: 3 mg/m 3

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 Freezing Point: 10% - 25" F

51% - 270 " F 51% - -30" F

Vapor Pressure:

Vapor Density: 3.4 Evaporation Rate: Less than 1

Water Solubility: 100% soluble

pH:

# 0.3 mm Hg at 77"F

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 (%)

LEL: Not applicable Reacts with most metals, especially when dilute, to give flammable, potentially

Hazards:

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

UEL: Not applicable

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

HEALTH HAZARD DATA

3

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:

Oral LD50

347 ppm in rats 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.

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.

Use appropriate

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

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Title:

MATERIAL SAFETY DATA SHEET

Subject:

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Linda Drury

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Creation Date:

3/17/1994 3:32 PM

Change Number:

22

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