CONTENTS

Introduction.....................................................................................................................................4 Sulfuric Acid Tanks.......................................................................................................................5 Recommended Materials of Construction..........................................................................6 Sulfuric Acid Corrosion Graph............................................................................................ 7-8 Assay of Sulfuric Acid...................................................................................................................9 Temperature-Baume Correction for Sulfuric Acid................................................10-13 Sulfuric Acid Conversion Tables.....................................................................................14-26 Oleum Conversion Table.......................................................................................................... 27 Specific Gravity & Acidity of Oleum...............................................................................28-29 Sulfuric Acid Concentration.....................................................................................................30 Calculating Mixtures of Oleum and Sulfuric Acid...........................................................31 Diluting Sulfuric Acid..................................................................................................................32 Heat of Dilution, Sulfuric Acid with Water........................................................................33 Vapor Pressure of Sulfuric Acid............................................................................................ 34 Vapor Pressure of Oleum..........................................................................................................35 Viscosity of Sulfuric Acid.......................................................................................................... 36 Viscosity of Oleum........................................................................................................................37 Thermal Conductivity of Sulfuric Acid Solutions........................................................... 38 Boiling Points of Sulfuric Acid and Oleum......................................................................... 39 Freezing Points of Sulfuric Acid and Oleum................................................................40-41

SULFURIC ACID

VISION AND VALUES STATEMENT

We are experts at converting energy into industrial chemicals on a large scale. We do it safely and efficiently to minimize our environmental footprint. We are a key part of our employees lives and valued by our community striving to treat these critical stakeholders with the utmost trust and respect while generating economic value in return for individual investment and community support. We recognize it is our customers who enable our existence, and we relentlessly pursue innovation to exceed their expectations in terms of quality, service, support, and delivery, nurtured by a culture that fosters commitment, excellence, and the unwavering passion of our employees. Building Value, Together

We will grow our business, leveraging the knowledge and capabilities of our employees to create value for customers, employees, shareholders, and the community.

Sulfuric Acid by Cornerstone

Cornerstone Chemical Company, originally American Cyanamid, has a long history of sulfuric acid manufacturing. Todays plant is an acid regeneration facility that produces sulfuric acid by the double absorption process. With an extensive logistics network,

Cornerstone can supply its customers with a wide range of grades and strengths of sulfuric acid and oleum providing delivery by tank truck, tank car, ship or barge. This manual presents the data most commonly needed by users of sulfuric acid, as well as general guidelines on storage and handling. Interested customers are invited to contact Cornerstone for additional information. We hope the information in this booklet will be useful and beneficial.

Cornerstone hopes the information in this booklet will be useful and beneficial. If you have any further questions, please contact us.

Sulfuric Acid Storage Tanks

GENERAL NOTES: 1. Tank to be constructed in conformance to API-620 standard. 2. Depending on size, tank shall be set on dunnage or solid concrete slab with slots set radially from center for leak detection. 3. Baked phenolic coatings are recommended for low iron pickup up to 93% concentrations. Above 93%, coatings will have shortened life. 4. Vacuum box test shall be performed to check tank floor welds. 5. Spill containment facilities must conform to all local, state and Federal requirements. 6. Fill nozzle should be located so as to avoid impingement of tank wall. 7. Size of tank should be 11/2 times normal quantity received. 8. Safety showers and eyewash stations must be provided at all operating areas.

Recommended Materials of Construction for Storage and Handling

The following recommendations are intended only to serve merely as a guide, since variations in temperature, velocity and other innumerate factors will affect corrosion rates. For more specific information, contact your Cornerstone sales representative. Sulfuric Acid Commercial, 93% & 98% Storage Tanks
Carbon steel with a minimum corrosion allowance with or without anodic protection. Direct inlet flows away from side walls.
1/8

Sulfuric Acid Electrolyte, 93.5%

Brick-lined steel. Steel lined with a baked phenolic such as Heresite. (Approx. life 5 years.) PPL lined steel, stainless steel 316L, Sch. 10 Chemical lead. Flanged joints. Design velocity for unlined pipe below 4ft./sec.

Oleum All Strengths

Carbon steelsame as Commercial Acid, TFE Lined pipe, and Alloy 20

Pipe and Fittings

Carbon steel (Sch. 80 for through 1/2 2 , Sch. 40 for 3 to 6.) Stainless steel 316L, Sch. 10 (1 to 4.) Butt welded and flanged joints. TFE, FEP or PPL lined steel for 93%. TFE or FEP lined steel for 98%. Design velocity for unlined pipe below 4ft./sec.

Carbon steelsame as Commercial Acid, TFE Lined pipe, and Alloy 20

Valves On Tanks

Globe, gate or plug with 150 lb. flanges. 2 minimum diameter. Alloy 20 with TFE packings, sleeves etc. Solid (not woven) TFE bonnet gaskets. Flanged Alloy 20 or TFE plug valves.

Same as Commercial Acid.

Same as Commercial Acid.

In Lines

Same as Commercial Acid. Alloy 20 centrifugal pumps with mechanical seals, sealess pumps (mag drive), and TFE Lined pumps. Alloy 20 metal components, ceramic rotating, and carbon stationary elements. Same as Commercial Acid. Same as Commercial Acid.

Same as Commercial Acid. Same as Commercial Acid. Alloy 20 metals components. Ceramic rotating and glass impregnated TFE or silicon carbide stationary elements. Same as Commercial Acid.

Pumps

Pump Seals

Gasket Materials

Garlock 7705, JM86A or equal. TFE, Blue Gylon 3504, and Fawn Gylon 3500

Same as Commercial Acid.

LEGEND PPL-Polypropylene TFE-Or PTFE, Polytetrafluroethylene FEP-Fluorinated Ethylene Propylene

Code for Sulfuric Acid Corrosion Graph

Materials in shaded zones have reported corrosion rate <20 mpy ZONE 3 3 ZONE 1 20Cr 30Ni 1 66Ni 32 Cu 20Cr 30Ni 1 62Ni 28Mo 66Ni 32 Cu 62Ni 28Mo Gold 2 Type 316 Lead 1 Al bronze 10% Molybdenum 1 Copper Platinum Gold Silicon iron Lead Tantalum Molybdenum Zirconium Nickel cast iron ZONE 4 Platinum Silver 20Cr 30Ni Tantalum 62Ni 28Mo 7 Zirconium Type 316 Gold 6 ZONE 2 Lead 3 Nickel cast iron 20Cr 30Ni 1 66Ni 32Cu Platinum 62Ni 28Mo Silicon iron 5 Type 316 Steel 1 Al bronze 10% Tantalum 1 8 Copper Zirconium Gold ZONE 5 Lead 3 Molybdenum 20Cr 30Ni 4 62Ni 28Mo Nickel cast iron Platinum Gold 9 Silicon cast iron Lead Platinum Silver Silicon iron Tantalum Tantalum Zirconium ZONE 6 10 62Ni 28Mo Gold Platinum Silicon iron Tantalum ZONE 7 Gold Platinum Silicon iron Tantalum ZONE 8 20Cr 30Ni 18Cr 8Ni 54Ni 15Cr 16Mo Gold Platinum Steel ZONE 9 20Cr 30Ni 18Cr 8Ni Gold Platinum ZONE 10 Gold Platinum

1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

No air <10% aerated <75C <20% at 25C <25% aerated at 25C <96% concentration >80% concentration <80% aerated <75C, <96% 20 to 50 mpy

Sulfuric Acid Corrosion Graph

Reproduced with permission of the National Association of Corrosion Engineers, Corrosion Data Survey, Metals Section.

Methods of Analysis for Sulfuric Acid

Acidity of sulfuric acid of composition not greater than 93% H2SO4 may be determined by specific gravity. The specific gravity of sulfuric acid solutions is often stated in terms of Baume scale which is defined for heavy liquids at 60/60F by the following formula: Be = 145 - 145__________
Specific Gravity

To determine the total acidity of a sample higher than 93% H2SO4 composition, a small sample is titrated with standardized sodium hydroxide, using methyl red as an indicator. For fuming sulfuric acid, a Dely tube is used to weigh and transfer the sample into distilled water prior to titration. The following is a more detailed description of the methods. Determination of Acidity by Baume Pour approximately 200 mL of sample into a 250 mL glass cylinder. Insert the appropriate Baume hydrometer into the cylinder, and let the hyrdrometer and the sample reach constant temperature. Read the Baume hydrometer and record the temperature of the sample. Correct the hydrometer reading for calibration error. Using the temperature Baumecorrection table, convert the Baume reading to its value at 60F. Refer to the appropriate table for percentage of acidity.

Temperature-Baume Correction for Sulfuric Acid

SUBTRACT correction when temperature is below 60 deg. F. ADD correction when temperature is above 60 deg. F.

Temperature-Baume Correction for Sulfuric Acid

Temperature-Baume Correction for Sulfuric Acid

Temperature-Baume Correction for Sulfuric Acid

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

SULFURIC ACID CONVERSION TABLES

OLEUM CONVERSION TABLE

SPECIFIC GRAVITY AND ACIDITY OF OLEUM AT VARIOUS TEMPERATURES

SPECIFIC GRAVITY AND ACIDITY OF OLEUM AT VARIOUS TEMPERATURES

Table I Sample Size for Determining Acidity of Sulfuric Acid Type of Acid 58% 78% (60) 93% (66) 96% 98% 100% Grams of Sample 2.5-3.0 + 0.001g 2.0-2.5 1.5-2.0 1.5-2.0 1.5-2.0 1.5-2.0

Titration of oleum 1. Accurately weigh (+ 0.001g) using a tared Dely tube approximately 1 mL of sample. Insert the long arm of the Dely tube into a 400-mL beaker containing 100 mL of CO2-free water. Flush the tube with 200 mL of additional water into the same beaker. 2. Add 3 drops of methyl red indicator and titrate with 0.5N sodium hydroxide to the methyl red end point. 3. Calculate as follows: Total acidity as % of H2SO4 = mL x N x 4.904 Grams of sample Where: mL = volume of 0.5N NaOH to methyl red end point N = normality of NaOH from Part B TOTAL IRON AS Fe, ppm. ALL GRADES ACID AND OLEUM Apparatus Pipets, Mohr, 10-mL. Flasks, volumetric, Pyrex, 100-mL. and 1-liter Electrophometer, Klett-Summerson or equivalent. Cell, 2x4x8-cm, for the above instrument. Filter, green, 525 nanometers, for photometer. Reagents Hydroxylamine hydrochloride, 1 molar. 1, 10-Orthophenanthroline monohydrate, 0.1% in water. Congo red indicator paper. Ammonium hydroxide, concentrated, reagent grade. Standard iron solution. Dissolve 0.1 g of pure iron wire in 10 mL of 10% sulfuric acid and 3 mL of reagent grade nitric acid. Cool, transfer to a one-liter volumetric flask and dilute to the mark with distilled water. Transfer a 10mL aliquot to a 100-mL volumetric flask and dilute to the mark. One mL of this solution contains 0.01 mg of iron. Procedures Preferred By means of buret, measure 2.0, 7.0, 10.0 and 20.0 mL of the standard iron solution, respectively, into five 100mL volumetric flasks. Add to each, 10 mL of 1 molar hydroxylamine hydrochloride solution. Heat to just boiling, cool and add a small piece of congo red paper and sufficient ammonium hydroxide to change the color of the paper to a bluish-red. Add 10 mL of 1, 10- orthophenanthroline (0.1% solution). Let the color develop for ten minutes, dilute to the mark with distilled water and mix. Adjust the zero of the photometer, using a blank of the reagents, the green filter (525 nm) and the 2-cm cell path. Record the dial readings obtained and plot them against the concentration (mg/100 mL). Use this plotted graph for all subsequent determinations of iron. Carefully pipet the prescribed sample volume (see Table II) into a 100-mL volumetric flask containing 15-20 mL of distilled water. During the addition, swirl the flask, tilting the neck away from the operator at all times. Add 10 mL of 1 molar hydroxylamine hydrochloride, heat to just boiling, cool and add a small piece of congo red indicator paper. Neutralize with ammonium until the congo red paper becomes a bluish-red color. Add 10 mL of 0.1% 1, 10-orthophenanthroline solution. Let stand for 10 minites and fill to mark with distilled water. Adjust the

zero of the photometer using a blank of the reagents, the green filter (525 nm) and the 2-cm cell path. Determine the reading of the sample and, from the chart, find the concentration of iron (mg Fe/100mL). Total iron as ppm Fe = mg Fe/100 mL x 10 _______ 3 Sample Wt. in Grams x 10 Alternate rapid control laboratory procedure Apparatus Pipet, Mohr, 5-mL Flasks, Volumetric, 100-mL Electrophotometer, Klett-Summerson or equivalent Cell, 2x4x8-cm, for the above instrument Filter, green, 525 nanometers for photometer Reagents Sodium acetate, NaC2H3O2 3H2O Hydroxylamine hydrochloride, reagent grade 1, 10-Orthophenanthroline monohydrate, reagent grade Mixed iron reagent. In a clean 25-litter bottle, weigh 544.8 grams of hydroxylamine hydrochloride and 5.587 grams of sodium acetate. Dissolve in distilled water. Dissolve 8 grams of 1, 10orthophenanthroline monohydrate in a liter of hot water and add to the first solution. Fill the bottle completely with distilled water and mix. Procedure Carefully pipet the prescribed sample volume (Tabe II) into a 100-mL volumetric flask containing 20-30 mL of mixed iron reagent. During the addition, swirl the flask, tilting the neck away from the operator at all times. Carefully dilute to volume with the mixed iron reagent. Mix well. Adjust the zero of the photometer using the mixed iron reagent. Convert Klett reading to mg Fe/100 mL, using chart previously prepared for iron determination (preferred procedure). Fe,ppm = mg Fe/100 mL x 10 ______ 3 Sample Wt. in Grams x 10 Table II Sample Size for Determining Acidity of Sulfuric Acid Type of Acid 58% 78% (60) 93% (66) 96% 98% 100% 20% Oleum 25% Oleum 27% Oleum 30% Oleum *Contains 5.0 Grams Sample Size, mL* 3.35 2.94 2.73 2.71 2.71 2.72 2.61 2.59 2.59 2.57
6 6

NOTE:

There are more sophisticated procedures for determining acidity and total iron as Fe (such as sonic analysis and atomic absorption). However, the procedures cited here are used more commonly. Additional information available upon request. NITRIC ACID, As ppm HNO3 Apparatus Nessler tubes, short form, Pyrex, 100-mL Beakers, 250-mL Buret, 5-mL Reagents 1. Ferrous sulfate solution. Dissolve 176.1 g of FeSO4 7H2O in 400 mL of distilled water. Add 400 mL of 60% sulfuric acid and mix. Transfer to a 1-liter volumetric flask and fill up to the mark with distilled water. 2. Standard HNO3 solution. Dilute one mL of concentrated reagent grade nitric acid (sp. gr. 142) to one liter with distilled water (1 mL = 0.001 g HNO3). 3. Sulfuric acid, conc., reagent grade. Procedure for Sulfuric Acid, 93-98% Cool a 250-mL beaker containing 3mL of distilled water in an ice water bath. Add 54 mL of sample while stirring carefully. Transfer to a 100-mL Nessler tube containing 1 mL of ferrous sulfate solution. Repeat the above procedure using reagent grade concentrated sulfuric acid, and titrate the blank with 0.1-mL increments of standard HNO3 solution until the color obtained is the same as that produced in the sample tube. Nitrates, as ppm HNO3 = (10) (mL of standard HNO3 solution). Procedure for 15-35% Oleum Cool a 250-mL beaker containing 30 mL of 75% sulfuric acid in an ice water bath. Add 54 mL of sample while stirring carefully. Transfer 52 mL to a 100-mL Nessler tube containing 1 mL of ferrous sulfate solution. Into another Nessler tube, add 1 mL of ferrous sulfate solution, 1 mL of water and 50 mL of reagent grade concentrated sulfuric acid. Titrate the blank with 0.1-ML increments of standard HNO3 solution until the color obtained is the same as that produced in the other tube. Nitric acid, as ppm HNO3 = (20) (mL of standard HNO3 solution).

SULFURIC ACID CONCENTRATION

To check H2SO4 content of a sulfuric acid solution, determine specific gravity and temperature. Point of intersection of these values on graph gives acid concentration on the diagonal lines. Examples: Specific Gravity Temperature H2SO4 Concentration 1 1.8050 93F (33.8C) 91.0% 2 1.8125 100F (37.8C) 93.9%

NOMOGRAPH FOR CALCULATING MIXTURES OF OLEUM AND SULFURIC ACID

Use the chart to determine the proportions of oleum and sulfuric acid needed to prepare a weaker oleum. For example, to determine what percentages of 97.75% H2SO4 and 30% oleum are required to produce 12% oleum, proceed as follows: 1. Connect 97.75% on scale A with 12% on scale C. Extend this line to intersect baseline A. 2. Connect 97.75% on scale B with 30% on scale D. Extend this line to intersect baseline B. 3. Connect the two points on baselines A and B. The required percentage of oleum and sulfuric acid can be read at the intersection of the line with the inclined axis, 55% oleum (30% free SO3) and 45% sulfuric acid (97.75%).

Diluting Sulfuric Acid

The rectangle method is a simple method to determine the amount of acids in different strengths of acid and water that must be used to prepare weaker solutions. First, draw a rectangle with intersecting diagonals. Place the concentration of the desired diluted solution in the center of the rectangle and the concentrations of the acids or water being mixed on the left corners. Subtract the smaller numbers from the larger and place them on the right corners of the rectangle. The numbers on the right represent the relative quantities by weight of the liquids being mixed that will provide a solution with the desired concentration. For example, if you wish to know how much 66Be acid and how many pounds of water

need to be mixed to provide 100 lbs of 52 Be acid, proceed as follows: 1. From the tables on pages 18-30, find the concentration (% H2SO4) of 52 Be acid which is 65.13. Enter this number at the intersection of the diagonals. 2. Next find the concentration of 66 Be acid, which is 93.19. Place this figure on the upper left corner of the rectangle. 3. Using 0 as the concentration of water, place this number on the lower left corner. 4. Subtract the figures along the diagonals and enter the results on the right corners. The results indicate that 65.13 lbs of 66 Be acid must be diluted with 28.06 lbs of water to yield 93.19 lbs of 65.13% diluted acid (52 Be). Since 100 lbs of diluted acid are desired, multiply by 100 or 1.073. 93.9 1.073 x 65.13 = 69.9 lbs of 66 Be acid 1.073 x 28.06 = 30.1 lbs of water 100.00 lbs of 52 Be acid

HEAT OF DILUTION, SULFURIC ACID WITH WATER

VAPOR PRESSURE OF SULFURIC ACID Merely determining temperature and concentration of the oleum solution will reveal vapor pressure values at a glance without resorting to tedious tabulations or confusing charts. Point of intersection of temperature (horizontal line) and concentration (vertical) indicates pressure value (curved lines) in pounds per square inch absolute (psia). Examples (Oleum): Temperature Free-SO3 Content Vapor Pressure 1 100F (38C) 30% 0.25 psia 2 125F (52C) 55% 6 psia

VAPOR PRESSURE OF OLEUM Merely determining temperature and concentration of the oleum solution will reveal vapor pressure values at a glance without resorting to tedious tabulations or confusing charts. Point of intersection of temperature (horizontal line) and concentration (vertical) indicates pressure value (curved lines) in pounds per square inch absolute (psia). 1 100F (38C) 30% 0.25 psia 2 125F (52C) 55% 6 psia

Examples (Oleum): Temperature Free-SO3 Content Vapor Pressure

VISCOSITY OF SULFURIC ACID Viscosity can be read quickly and accurately by determining temperature and concentration of the sulfuric acid. From point of intersection of temperature reading (move across, horizontally) and concentration (move up, vertically). Viscosity value in centipoise (cps) can be determined by relating to curved lines. Examples Temperature Concentration Viscosity 1 140F (60C) 60% 3 cps 2 100F (38C) 80% 12 cps

VISCOSITY OF OLEUM Viscosity can be read quickly and accurately by determining temperature and concentration of the oleum. From point of intersection of temperature reading (move across, horizontally) and concentration (move up, vertically). Viscosity value in centipoise (cps) can be determined by relating to curved lines. Examples Temperature Free-SO3 Content Viscosity a 120F (49C) 40% 19 cps 1 b 100F (38C) 20% 19 cps 2 100F (38C) 80% 12 cps

THERMAL CONDUCTIVITY OF SULFURIC ACID SOLUTIONS Only the most easily obtained values (acid temperature, concentration) need be determined. Intersection of these values on base coordinate chart indicates Thermal Conductivity [Btu/(hr) (ft2)(F/ft)] directly. Examples Temperature Concentration Thermal conductivity 1 100F (38C) 40% 0.300 2 197F (92C) 85% 0.255

BOILING POINTS OF SULFURIC ACID/OLEUM

FREEZING POINTS OF SULFURIC ACID/OLEUM SYSTEMS

FREEZING POINTS OF SULFURIC ACID/OLEUM SYSTEMS

IMPORTANT NOTICE: The information and statements herein are believed to be reliable but are not to be construed as a warranty or representation for which we assume legal responsibility. Users should undertake sufficient verification and testing to determine the sustainability for their own particular purpose of any information or products referred to herein. NO WARRANTY OF FITNESS FOR A PARTICULAR PURPOSE IS MADE. Nothing herein is to be taken as permission, inducement or recommendation to practice any patented invention without a license. CUSTOMER SERVICE Fortier Complex - U.S. (Louisiana) Telephone: 504-431-6189 or Toll-free: 1-800-236-0977 After office hours, please call: 504-431-6353 or 504-431-9511