New Handbook CASO - 2013 Rev2

Products, Applications, Safety, Handling and Storage, Characteristics, Methods
SOLVAY CASO
CALCIUM CHLORIDE
HANDBOOK
Table of contents
1 SOLVAY, THE COMPANY ............................................................................................... 4 1.1 History ..................................................................................................................... 4 1.2 Solvay Mission and Vision .................................................................................... 4 1.3 Solvay Values ......................................................................................................... 4 1.4 Solvay Code of Conduct ........................................................................................ 5 1.5 Customers............................................................................................................... 5 1.6 Suppliers ................................................................................................................. 5 1.7 Competitors ............................................................................................................ 5 1.8 Shareholders .......................................................................................................... 5 1.9 Public authorities ................................................................................................... 5 1.10 General public ........................................................................................................ 5 CASO CALCIUM CHLORIDE ......................................................................................... 6 2.1 Production Process ............................................................................................... 6 2.2 The benefits ............................................................................................................ 7 2.3 Three commercial grades ...................................................................................... 7 2.4 Production Plant..................................................................................................... 8 MAIN USES OF CASO CALCIUM CHLORIDE ............................................................. 9 3.1 Food & Agro-Food industry .................................................................................. 9 3.2 Animal nutrition .................................................................................................... 11 3.3 Serving the chemical industry ............................................................................ 12 3.4 Oil & Gas Industry ................................................................................................ 12 3.5 From earth to concrete ........................................................................................ 13 3.6 Helping the environment ..................................................................................... 14 3.7 Metallurgy ............................................................................................................. 15 3.8 Domestic dehumidification ................................................................................. 15 3.9 Winter road treatment .......................................................................................... 15 3.10 Anti-Dust treatment .............................................................................................. 19 SAFETY & ENVIRONMENT ........................................................................................... 21 LOGISTICS ..................................................................................................................... 22 5.1 Packaging ............................................................................................................. 22 Handling and Storage ..................................................................................................... 22 6.1 Dry calcium chloride storage bins ..................................................................... 22 6.2 Dry calcium chloride conveyors and elevators ................................................ 23 6.3 Storage tanks for liquid calcium chloride ......................................................... 23 6.4 Dissolving CASO ............................................................................................... 23 Chemical-physical properties of CASO calcium chloride .............................................. 25 7.1 Properties of Anhydrous calcium chloride........................................................ 25 7.2 Properties of the hydrates of calcium chloride ................................................. 25 7.3 Properties of calcium chloride solutions........................................................... 26 7.4 Solubility ............................................................................................................... 31 7.5 Apparent solidification vs. actual freezing temperatures ................................ 33 7.6 Boiling temperatures ........................................................................................... 34 7.7 Vapor pressure ..................................................................................................... 34 7.8 Atmospheric moisture absorption by commercial calcium chloride ............. 37
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SOLVAY CASO calcium chloride HANDBOOK
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7.9 pH of calcium chloride solutions........................................................................ 39 7.10 Surface tension .................................................................................................... 42 7.11 Viscosity................................................................................................................ 44 7.12 Dilution of calcium chloride solutions ............................................................... 45 7.13 Specific heats ....................................................................................................... 47 7.14 Heat of solution of calcium chloride .................................................................. 47 7.15 Heat of dilution and heat content of calcium chloride solutions .................... 48 7.16 Thermal conductibility ......................................................................................... 50 7.17 Specific problems of technical calcium chloride solutions............................. 51 8 ANALYTICAL METHODS ............................................................................................... 56 8.1 Total Calcium (Ca) EDTA potentiometry test ................................................. 56 8.2 Alkalinity as Ca(OH)2 Phenolphthalein test .................................................... 56 8.3 Sulfates (CaSO4) Ionic chromatography method ........................................... 57 8.4 Iron (Fe) Spectrophotometric test ................................................................... 57 8.5 Water insoluble matter Gravimetric method .................................................. 58 8.6 Turbidity spectrophotometer test.................................................................... 58 8.7 Granulometry automatic sieve test ................................................................. 58
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SOLVAY, THE COMPANY
1.1 History
The story of the Solvay group began in 1861, when Ernest Solvay discovered the key to the industrial manufacture of soda ash using sea salt, ammoniac and carbonic acid. In 1863, Ernest Solvay patented a revolutionary ammonia-soda process for producing sodium carbonate which is still widely used today in the glass, washing powder and flue gas cleaning industry. The first soda factory started operating in Couillet, Belgium in 1865. From 1870 to 1880, Solvay promoted the global expansion of the company. Factories were set up in Belgium, France, England, Germany, Russia and the United States. Today, Solvay is an international industrial Group active in chemistry, with three sectors of activity: Chemicals and Plastics and Rhodia. The latter was acquired in September 2011. Sustainability is at the heart of Solvay's strategy. It is based on a systematic approach taking into ccount the expectations of our key stakeholders, and ibuilt on financial, environmental and societal responsibility. The Solvay Groups philosophy is unaltered: realize sustained growth with leading positions and maintain a conservative financial structure. A Group Vision and Strategy to ensure profitable and sustainable growth through:
a strong leadership in all of our activities an important presence in emerging markets the control of cyclicality of activities high value added alignment on megatrends which ensure the sustainability of performance and steer future developments
1.2 Solvay Mission and Vision

Building on its scientific, technical and commercial expertise in Chemistry, and aware of its societal responsibilities, Solvay provides innovative products and services to create sustainable and ever- increasing value to our customers, shareholders and employees. Solvay is an independent, ethical and responsible global industrial Group with a balanced portfolio of sustainable, profitable and growing businesses, managed in accordance with societal and environmental issues:
Amongst the world leaders in selected markets and products either alone or with sound Valued by its customers as a highly competent, reliable and competitive solution provider With a clear, motivating organization, through dialogue, developing and empowering people
and teams through rewarding and challenging jobs employees and of the community at large environmental progress. complementary business partners
Acting as good corporate citizens, caring for the environment, health and safety of its Open to the expectations of the outside world, and contributing to economic, societal and
1.3 Solvay Values

Solvay firmly believes in ethical behaviour, respect for people, customer care, empowerment and teamwork.
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1.4 Solvay Code of Conduct

Solvay's Code of Conduct lists and defines the values that serve as the framework for the Groups decisions and operations and is inspired by international conventions such as the Universal Declaration of Human Rights, the Convention on the Rights of the Child, and the conventions of the International Labour Office Organization. Solvay expresses its commitment to sustainable and responsible practices by taking into account the sustainable growth of its business, and its good reputation within the communities in which it operates.
1.5 Customers
Solvay is committed to meeting the needs of its customers by delivering products and services on time, in the quantity, and at the quality level agreed upon.
1.6 Suppliers
Solvay's relationships with suppliers are based on trust and partnership. Suppliers are selected, without discrimination, through open competition and on the basis of an objective and verifiable evaluation of their performance as well as of their ethical performance in matters of safety, respect for the environment and childrens and human rights.
1.7 Competitors
Solvay values and embraces fair and open competition as essential to maintaining the dynamism of free enterprise and creating value for society at large.
1.8 Shareholders
Solvay fully and accurately informs its shareholders of all actions, events or decisions that could reasonably have a significant effect on its decisions and performance. It is fully compliant with all applicable corporate governance rules.
1.9 Public authorities

As a responsible producer, the Group works closely with public authorities to reduce any negative environmental effects due to accident or discharge. In the case of an incident unrelated to Solvay, the Group will still provide its resources and expertise to emergency responders and public authorities requesting assistance.
1.10 General public

Solvay actively fosters open dialogue between its public and its constituents in order to achieve mutual understanding and benefit.
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CASO CALCIUM CHLORIDE
CASO Calcium Chloride is one of Solvay's oldest products, and it still remains important today. Over the years, Solvay has adapted the applications of CASO to meet the demands of users as diverse as the agricultural and food & feed industries and civil engineering. It is also used extensively in the oil industry, in water treatment processes, for treating roads in winter and summer, and for domestic and industrial dehumidification
2.1 Production Process

CASO SOLVAY is produced using two different lines. The oldest one is used for producing Flakes, Powder and Solutions, while, since 2007, a new production line has been started up for producing anhydrous product in granular form. The oldest traditional production line is refining and concentrating calcium chloride brine at low concentration coming from the nearby SOLVAY Soda Ash plant up to 78% CaCl2 in weight, using six different sectors working in series and in parallel. 2NaCl+CaCO3 Na2CO3+CaCl2
The qualities of CASO Solvay produced according to this process are as follows:
Liquid CASO 2529% and 3537% technical grade, Liquid CASO 3537% Food grade, Solid CASO min 75% in flakes, food, feed and technical grade, and Solid CASO min 75% in powder, feed and technical grade
During the production process, the calcium chloride solution is depurated and cleared from the main impurities (insoluble substances, hydrated lime, calcium sulphate, sodium chloride), so as to avoid any possible alteration of the final product. Once all the impurities have been eliminated, the calcium chloride solution circulates in evaporators and tanks where, with the addition of vapours at different pressure and temperature, it undergoes a process of evaporation and concentration to reach a content of 73% in weight. At this step, the product is still liquid. During the following step, a plunging wheel is immerged into the 73% calcium chloride solution: as a consequence of the internal cooling a solid layer will cover the surface of the wheel and finally the liquid product becomes solid. At this stage, the solid product turns into flakes (73%) which after desiccation in a dryer, by adding warm gases, will reach the typical concentration of 77%. The desiccated calcium chloride, before being stocked in silos, packed and finally being sold, is refrigerated by an air scrubber at first, then cleaned from dust and finally conditioned, in compliance with the sales specification. The product has now the shape of 'white flakes', measuring between 3x3 and 10x10 mm as dimension and with an average thickness of 0,5 - 1,5 mm. After the cleaning and dehumidification treatment, based on the introduction of hot air at the entrance of the silos, the calcium chloride flakes are totally free from any dust particles. Then they are collected and become a 'Final Product' which will be stocked, packed and sold as solid CASO . During the intermediate step of the production cycle, a part of the liquid calcium chloride at 50% in weight is diluted with de-mineralized water, thus obtaining CASO 2529% and 3537% solutions, which, after proper decantation and filtration, are stored in tanks and finally sold.
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CASO Granules are produced in the Rosignano Plant using a new production line, where the 35% CaCl2 solution, generated by dissolving limestone with hydrochloric acid, is concentrated by evaporation of water up to 95% in a fluidized bed granulator. The qualities of the obtained CASO product are as follows: CASO Granules, CaCl2 min 94% technical grade, and CASO Standard Granules min 90% technical grade.
2.2 The benefits

CASO SOLVAY is characterised by a certain number of remarkable properties which determine its many applications. Low freezing point with water: in conjunction with water, CASO forms a solution that will not freeze until it reaches a temperature of -51.6C; Exothermic dissolution: when it dissolves in water, CASO gives off heat (dissolving 1 gram of CASO Granules in 100 g of water would increase the temperature of the water by 1.65 C., 20% more than CASO FLAKES); High hygroscopicity: CASO absorbs humidity from the atmosphere even during very dry weather; Deliquescence: CASO dissolves in water absorbed High specific gravity: a solution of 40% CaCl2 produces a specific gravity of 1.4 kg/dm3 at 15C.
2.3 Commercial grades

Each product grade is identified by a specific batch number which guarantees the traceability of its production. Normally, for each delivered product, a Certificate of Conformity (CoC) is issued affirming that the product respects sale specifications. A Certificate of Analysis (CoA) could be issued on demand only if it has been agreed with our sales department in advance.
Technical Grade
CASO TEC, calcium chloride technical grade, can be used in various applications in industrial, public and private sectors. It is available in Flakes, Powder and Liquid forms (25 36% solutions)
Food Grades
CASO FOOD Flakes is a dihydrate calcium chloride food grade of mineral origin, and CASO FCC SOLUTION is a 36% CaCl2 solution. In the context of the European Regulation N 1333/2008 on food additives, permitted for use in foodstuffs, and European Regulation 231/2012, laying down specific purity criteria for food additives other than colours and sweeteners, both products are characterized by the European Number E 509 referring to 'calcium chloride'. CASO FCC Flakes is a dihydrate calcium chloride food grade of mineral origin. According to the International Numbering System (INS) for food additives, CASO FCC Flakes is characterized by the INS Number 509 referring to "calcium chloride". CASO FCC Flakes is compatible with the food uses for which the Food Chemicals Codex (8th Edition) specifications are required, but does not constitute a food additive pursuant to European Regulation N 1333/2008 as amended. A Hazard Analysis Critical Control Point (HACCP) system is implemented in our manufacturing plant and it consists of applying the following principles: the conduction of a hazard analysis and the identification of preventive measures; the determination of Critical Control Points (CCPs), the establishment of critical limits, monitoring procedures, corrective actions, record keeping and documentation procedures (ensuring traceability and claims treatment) and the establishment of verification procedures.
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Furthermore, our manufacturing plant is registered by the competent authority and a sanitary/hygiene authorisation was issued for the manufacture, storage and marketing of the product (Autorizzazione Igienico sanitaria N 111 Site Registration Number: IT 090 49017-0385).
Feed Grades
CASO FEED, calcium chloride is a feed material of mineral origin for animal nutrition. It is available in Flakes and Powder forms. Putting in practice the rules of Regulation 183/2005/EC, SOLVAY has registered its production plant as producer of industrial calcium chloride of mineral origin for animal feed, as indicated in the Italian Ministerial Decree of 13 of November 1985, to the local Authority USL 6 of Livorno (Italy) in compliance with Decree 6610/2005 issued by the Tuscany Region, adopting the rules of Articles 5 and 9 of the Regulation 183/2005/EC itself. To assure the safety of the product during its transportation, SOLVAY has defined some internal procedures that determine the acceptance criteria of the trucks that will be used for the deliveries, using the GMP+ rules established by the Dutch Product Board Animal Feed as reference, and has obliged all transporters to register themselves as feed operators to the competent authorities.
2.4 Production Plant
Company name: Address: Zip Code: City: Country: Phone: Fax:
Solvay Chimica Italia S.p.A. Via Piave 6 I-57013 Rosignano Solvay (LI) Italy +39 586 72 11 11 +39 586 72 17 28
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MAIN USES OF CASO CALCIUM CHLORIDE
Some application of these products may be regulated or restricted by national or international standards (e.g. for food additives, feedingstuff, water treatment, the cosmetic or pharmaceutical industry, etc). The buyer and the eventual user, in his sole and entire liability, shall respect those standards, orders of any relevant authority, and all existing patents and intellectual properties rights; and shall comply with the laws and the regulations applicable to our products and/or to his activity. The buyer and ethe eventual user must independently determine the suitability of this product for any particular purpose and its manner of use.
3.1 Food & Agro-Food industry

CASO calcium chloride is used in many applications, such as agriculture, foods, treatment of raw water. Agriculture For many years, the agricultural industry has been employing various products to improve the quality and productivity of arable land. Confronted with restrictive economic conditions, fertiliser manufacturers are using an increasing quantity of industrial products available in powder, granular or liquid form. These are mixed to provide the ideal chemical composition for a particular crop (nitrogen, phosphorous, potassium, calcium, sulphur, sodium, magnesium and oligo-elements). To make these products easy and safe to handle, they are produced in granular form. One of the products generally used for granulation is calcium chloride. Calcium chloride is a viscous, adhesive product. When it comes into contact with powders, it imparts a degree of cohesion. In the granulator (a sort of heated rotating drum), the sticky powders agglomerate into small granules. When the granules are dry, they are packaged. The intensive cultivation practised by farmers alters the quality of agricultural products; new diseases resulting from a poor mineral balance in the soil are appearing. Plants which grow rapidly are generally most affected by these new phenomena. Many studies have highlighted the primary role of calcium in the quality and storage characteristics of agricultural products. Calcium, which is present in large quantities in nature, migrates with difficulty in soil, plants and trees. It contributes to the composition and solidity of plant cells and therefore constitutes an important nutritional element for plants. A calcium deficiency induces weakness of the plant cell walls, which is manifested by a loss of weight, lack of firmness and the rapid deterioration of fruit and vegetables. It has been demonstrated that bitter pit in apples, browning in the hearts of endives and apical fever in tomatoes result from a lack of calcium. Treatment with calcium chloride strengthens the natural defences of plants against disease.
CASO calcium chloride plays a preventive role by first attacking the causes of the problem.
Dairy products and cheese CASO Food grade calcium chloride is used in the dairy sector to increase the calcium content of dairy products. It is an interesting product because its use is legally authorised and because of its good price, the great bio-availability of calcium, its very small alteration of the 'taste' profile of the foods it supplements. Finally, it can be added as such. It is recommended to check the pH of milk when adding calcium chloride. More specifically, at a pH below 5.2, milk proteins coagulate. Beyond 7.5, the taste of milk is modified.
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Cheese production is an enzymatic process in which casein or rennet (enzyme of the stomach of an unweaned calf) is made to react with milk. Coagulation usually takes place at a temperature of about 30C. Adding calcium chloride accelerates the phenomenon while economising on the rennet content (more expensive than CaCl2).
Finally, when hard cheese production is finished, it may be soaked in a solution of CASO Food
Grades calcium chloride in order to increase the hardness of the outside crust. Storage Before being canned, fruits and vegetables undergo a number of treatments to stabilise their behaviour before and during their preservation period (cooking, sterilisation, lowering of pH to reduce any bacterial activity, etc ...). This type of treatment usually entails an improvement of the treated foods. To give them certain firmness, calcium chloride can be added to the blanching water or to the can. CASO Food Grade Calcium chloride is used in preserves as an agent for improving the appearance and firmness of preserved products (carrots, celery, gherkins, onions, stuffed and unstuffed olives, peas, peppers, canned potatoes, salsify, tomatoes, meat, apple pure and frozen products for rapid cooking). CaCl2 strengthens the external surface of such products and improves their appearance and behaviour when preserved. It is also increasingly used in other applications as a substitute for more costly calcium salts used for the same purpose. Calcium is an important plant nutrient as it contributes to cell strength. Increasing the calcium content during preparation or preservation improves the firmness of products (e.g. soft or hard peeled tomatoes) or their cooking characteristics in a microwave oven. Refrigeration Thanks to the low freezing point of its solutions, CASO Calcium chloride is used in freezing plants, as Food Processing Aid, as a refrigerant in ice cream and frozen dessert manufacturing Beer and soft drinks: remineralisation of water The use of calcium chloride for water remineralisation is intended as Food Processing Aids. Soft drinks manufacturers and breweries are confronted with significant differences in the quality of water supplied to them. This can result in variations in taste between factories or between production periods. The solution to this problem is to totally demineralise the water and then carry out a controlled remineralisation. For drinking water distribution companies, the chemical composition of drinking water depends on the sources geotechnical conditions. The same applies to its calcium bicarbonate content. The latter is responsible for a great deal of the corrosion in drinking water pipes. Water with a low pH may have its corrosive effect partially offset by the presence of a certain quantity of calcium carbonate which acts rather like a protective film for pipework (increasing hardness). The purpose of re-mineralising water is to increase its calcium chloride content. This has two precise applications: calcium chloride or tartar can slightly alter the taste of water and also helps to protect pipes from corrosion: CaCl2 + 2 NaHCO3 CaCO3 + 2 NaCl + H2CO3
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Recovery of tartaric acid Tartaric acid and its salts are used in the food, cosmetic, pharmaceutical, textile, colourings and printing sectors. CASO Calcium Chloride enables all of the residuary substances, produced in making wine from grapes, to be valorized. These residues are generally rich in tartrates which, after reacting with Calcium Chloride, form calcium tartrate which is easy to transport and to use wherever it is required to produce synthetic tartaric acid. Alginates Alginates are raw materials used in the following sectors: food and food processing (food additives, emulsion stabilisers in jellies, artificial creams for pastries and dietary products), industrial (finishing yarns and fabrics, sizing yarns, soluble alginate yarns used in lace making, thickening printing dyes), cosmetics (shampoo with oligo-elements, make-up removers, various creams), pharmaceuticals (dressings, powders, compresses). They are manufactured from specially treated brown algae. Although there are hundreds of species of brown algae, only a few are used for alginate extraction. The algae are attacked by caustic soda and sodium carbonate (alkaline digestion of the algae). The product obtained (soluble sodium alginate) is brought into contact with a 1 to 10% solution of CASO calcium chloride to produce calcium alginate (insoluble). This calcium alginate is placed in an acid environment (HCl); this produces solid alginic acid. Finally, this acid is neutralised with sodium bicarbonate and sodium carbonate to create pure, solid sodium alginate. Consumption of anhydrous calcium chloride is estimated at 30 kg per ton of algae. Note that alginic acid, calcium, ammonium, potassium and magnesium alginates, etc., are also known as algins.
3.2 Animal nutrition

Calcium chloride is classified as feed material for animal nutrition according to European Regulation 575/2011.
SOLVAY is manufacturing and placing on the market CASO FEED dihydrate calcium chloride, feed material of mineral origin in conformity with the European Directive 2002/32/EU and its amendments on undesirable substances in animal feed, and certifying all the produced batches with Certificates of Conformity.
With the aim to guarantee both traceability and safety of the entire food chain, SOLVAY, in the context of the European Regulations 178/2002/EC and 183/2005/EC, has implemented an HACCP system for its manufacturing plant. Putting into practice the rules of Regulation 183/2005/EC, SOLVAY has registered its production plant in Rosignano (Italy) as producer of industrial calcium chloride of mineral origin for animal feed, as indicated in the Italian Ministerial Decree of 13th of November 1985, to the local Authority USL 6 of Livorno (Italy) in compliance with Decree 6610/2005 issued by the Tuscany Region, adopting the rules of Articles 5 and 9 of Regulation 183/2005/EC itself.
CASO FEED is used in dairy cow nutrition. During the transition lactation period of cows and pigs, calcium chloride aids to reduce the incidence of milk fever and hypocalcaemia disorders. Orally feeding of calcium chloride in lambs, sheep and goats can precipitate oxalate, eventually metabolized by the rumen, thus stimulating diuresis and avoiding renal diseases. It acts as calcium source in the cationanion balance (CAB)
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3.3 Serving the chemical industry

CASO calcium chloride is used in many chemical applications. The chemical industry often needs calcium and chloride ions for its various applications. The industry also requires certain physicochemical properties such as solubility and viscosity, which CASO can provide. Plastics CASO Calcium Chloride is used in the manufacture of certain synthetics including MBS and ABS. Raw plastics rarely offer the characteristics required of them: impact resistance, temperature, ultraviolet rays... That is why in the case of PVC, for example, MBS is added to increase its impact resistance. PVC made in this way is used principally in the manufacture of bottles. ABS is a synthetic resin used among other things in the manufacture of car bumpers. Calcium chloride is added in liquid form to an emulsion (an intimate mixture of two immiscible products). After flocculation the required resin is obtained. Added to PVC, MBS resin increases the products impact resistance and the PVC produced in this way is largely used in the manufacture of bottles. ABS is a resin used primarily for manufacturing car bumpers. Fluorescent powders Fluorescent powders are used to make lighting tubes. They form a film inside these tubes which converts ultraviolet rays generated by electric sparks into visible light. CASO Calcium Chloride is used in the composition of fluorescent powders.
3.4 Oil & Gas Industry

Oil drilling Oil is generally found at very great depth in the ground. In order to reach it, it is necessary to drill wells several thousand meters deep. When a hole is made in the ground, the sides tend to crumble. When drilling to a great depth, this must be avoided. There are numerous ways of achieving this, the main one being using high density solutions. The chemical composition of the used solution depends on the geotechnical drilling conditions (type of strata to be drilled, temperature, risk of encountering pockets of gas under pressure, size of the operation). CASO calcium chloride is one of the products employed for this technique, but its use is limited. The drilling-mud specialist prepares the ideal mixture depending on the depth to be attained and the type of ground to be drilled. To prevent the sides of a drill hole from collapsing, the liquids used must display certain characteristics: high density: dense liquids provide better support; viscosity: they must not penetrate too easily into porous soils stability at high temperatures: they must not decompose at high temperatures; ability to raise excavated material; insensitivity to the chemical environment: a reaction with rock could modify one of the characteristics mentioned above.
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To get the highest productivity out of an oil or gas well the right completion fluid has to be chosen. Once the drill has hit the production zone, the work isnt over. To obtain maximum flow and protect the zone itself, the proper completion fluid is all important. Virtually any liquid that is free of solids can function as a completion fluid but matching the density, flow and pH content to the characteristics of the hole will lengthen the life of the production zone. Finding a completion fluid that complements the characteristics of a particular oil or gas well increases the capacity of the well. It also makes site preparation easier and limits site erosion and/or possible damage to the site. The right completion fluid may also make it easier to repair a well should that become necessary. When its time to clean up and close down the well, having chosen good completion fluids will make those jobs easier, too. CASO calcium chloride is used extensively as drilling fluid and heavy oil drilling fluids. The innate properties of calcium chloride make it optimal for snubbing because its safe, economical, reusable and enhances the likelihood of maintaining well production after servicing. Drying Hydrocarbons Sometimes oil contains water which tends to corrode manufacturing and storage plants and causes turbidity in oil products. Oil refining companies employ various means for getting rid of the water, including absorbent resins, salt and CaCl2
CASO Calcium chloride is hygroscopic (absorbs humidity) and deliquescent (liquefies in the absorbed water). The absorbed water, together with the absorbed product, forms a solution much denser than oil products and is therefore deposited at the bottom of the tank.
3.5 From earth to concrete

1885: first application in civil engineering! Since then, things have improved greatly. CASO calcium chloride is used as an additive for road foundations and the beds of railway tracks. It also represents a simple solution to a complex problem linked to road constructions: it freezes the soil. CASO calcium chloride solution acts as an accelerator and anti-freeze for concrete. Cement There are three major applications for calcium chloride in cement industry: lowering the melting point of minerals during clinkering; reducing the alkaline content of cement; accelerating the setting and hardening of cement after it has been laid In cement making, selected raw materials are melted and then crushed after cooling (clinker) and mixed with quicklime. Introducing 2 to 3% Cl- into the kiln reduces the clinkering temperature of materials, which results in savings of 20 to 30% on the energy required for its manufacture. Moreover, calcium chloride accelerates the setting and hardening of laid concrete (see concreting). Finally, certain types of cement react with the aggregates with which they are mixed. The products of such reactions cause dilation leading to disorders in the structure in which they are incorporated. CASO Calcium chloride is added to the clinker kiln in order to sublimate the reaction products that are formed. Concrete making Fresh concrete easily takes on the desired shape and, when hardened, retains this shape and fulfils the requirements for which it was designed. Over the years, the industry has produced additives capable of meeting the growing need for workability, strength and economy. CaCl2 possesses several useful properties which have been exploited in concreting since 1885.
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Calcium chloride accelerates hardening in concrete within the first few hours after casting. Because of this, the initial strength obtained over the first few days is considerably increased. The addition of calcium chloride reduces the normal setting time for concrete by more than 50% and accelerates hardening. This property of calcium chloride is even more useful when the ambient temperature is low. Cold hinders, or even prevents, cement hardening, which can cause irreparable damage to green concrete. A fall in temperature slows down setting and hardening. When the temperature falls to between +5C and +10C, depending on the type of cement employed, calcium chloride should be used. At around 0C incorporating calcium chloride prevents concrete from freezing and enables concreting to continue. Note that calcium chloride is practically the only really satisfactory product for combating the effects of freezing on fresh concrete (max. -5C). European standards (ENV 206) concerning concrete additives have moved against the use of CaCl2. It is totally banned in certain countries (NL - D - N - S). Note that in other countries, the use of calcium chloride is becoming ever more restricted: 1% for non-reinforced concrete, 0.4% for reinforced concrete and 0.2% for pre-stressed concrete. Road construction The following technique is used in the construction and repair of roads: ever harder layers (subfoundations or foundations) are laid on top of the raw earth and are covered by a flexible (black hydrocarbon) or rigid (clear concrete) coating. The quarries which provide these materials are beginning to be exhausted and are seeking ways of using lower quality materials.
CASO calcium chloride significantly improves the qualities of most materials to which it is added. Selected grades of hard core mixed with 1.5% liquid CaCl2 display significant advantages for the following types of application:
very easy laying and profiling using a finisher (laying machine); not susceptible to frost or damage from winter cold; reduced energy requirements for compacting and faster execution; holes in foundations caused by work on the highway can be sealed without joint or risk of settlement; does not crack or shrink with no rising of cracks; better carrying capacity. Refrigeration CASO calcium chloride is used in refrigeration plants for freezing soil. When geotechnical (poor soil quality) or local (presence of a building on the surface) conditions are not suitable for some types of excavation, freezing the soil is the technique that is used. In fact, frozen soil behaves like rock which then requires drilling through. After the required work has been carried out, the soil is simply allowed to thaw. Soil consolidation When constructing a basement, it can happen that the geotechnical conditions are not suitable. In this way, when you dig a hole in the ground, the walls tend to fall in. This phenomenon can be avoided by calling on solutions with well defined characteristics. CASO calcium chloride is used in this area as a flocculating agent for excavating mud.
3.6 Helping the environment

CASO calcium chloride contributes to a better environment by treating effluent and desalinating soil. Treatment of effluents Current industrial trends aim to work in an increasingly ecological way. Water containing excess fluoride is harmful for human beings, animals and the environment. However, a limited level of fluoride in drinking water has been demonstrated to help to combat dental decay and presents no danger to health.
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By adding CASO calcium chloride to fluoride effluent, fluorinated water can be purified. Fluorine is precipitated in the form of calcium fluoride (CaF2), which is only slightly soluble in water. The low -11 solubility of CaF2 (kps=3.410 ) at 18C means that at this temperature, 16 mg of CaF2 can be dissolved in a litre of distilled water, which represents a fluorine content of around 8 mg/l, below environmental standards of 10 mg/l. A good pH level (7-9), obtained by adding lime and an additional dose of CaCl2, makes it possible to reduce the dissolved CaF2 content even further. Residual water contains other cations and anions which influence the solubility and structure of calcium fluoride crystals. Furthermore, flocculation can improve fluorine elimination. The presence of flocculating ions (aluminium, iron and silicates) makes it possible to purify to a level of less than 2mg/l. Some industries produce dissolved sulphates that they do not require. It is desirable to eliminate these materials by insolubilising them thoroughly. Finally, CASO calcium chloride is an attractive flocculating agent for breaking down certain emulsions. Soil desalination After major flooding by sea water, the excess of sodium deposited by the water greatly reduces the fertility of the soil. In fact, sodium is one of the elements which compete with the atoms absorbed by plants when they grow. Moreover, sodium reacts with certain soil types and leaves them waterproofed, thereby preventing the soil from breathing. The correct amount of CASO Calcium Chloride scattered on the soil improves the ionic and osmotic balance, and hinders soil crusting, with the result that the soil is able to breathe better.
3.7 Metallurgy
CASO is regularly used in metallurgy, especially for: iron: reduces corrosion and any attack on refractory surfaces induced by the pH of the mineral used in the blast furnaces. It also helps control the level of sulphur, alkalis (oxides, Na, K) in finished products. Titanium: used as a chemical intermediary in the manufacture of titanium oxide (white colouring) used in the production of paint. Zinc-tungsten: used as a chemical intermediary. Sodium: lowers the fusion point of sodium during the electrolysis of salt. Non-ferrous metals: mixed with salt, lowers the fusion point of minerals
3.8 Domestic dehumidification

Humidity is not always welcome in what you are doing, and can represent a big problem in many cases, but it can be eliminated with CASO calcium chloride. The air is a vehicle for humidity, and therefore it can bring or remove humidity.
Combined with a drying system, either industrial or domestic, CASO SIEVED FLAKES can dry out walls or atmospheres: being both hygroscopic and deliquescent, it absorbs the water and can deposit in the form of a thick liquid at the base of the dryer.
3.9 Winter road treatment

Winter temperatures often result in snow or ice, making live difficult for traffic on roads. Since the 1930s, calcium Chloride has been used to melt snow and ice or to prevent water from crystallising on the road. CASO Calcium Chloride is the fastest, most effective ice melt product available on the market. It melts ice to -32C. CASO Calcium Chloride is a product characterised by a compounding point with water (eutectic), which enables the mixture to be kept liquid well below freezing point. Thanks to its hygroscopicity, CASO Calcium Chloride absorbs any water present in the air and eventually dissolves itself releasing heat (exothermic reaction), thus accelerating the thawing process. Liquid CASO
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Calcium Chloride has a viscosity that permits it to adhere better to the road surface. Vegetation, corrosion and concrete performances compare favorably to competing ice-melt materials, including magnesium and potassium chloride.CASO Calcium Chloride is used in different forms and concentrations: technical flakes or granules, sprayed on the roads directly technical liquid as wetting agent with rock salt or alone. No other ice melting product works on snow and ice better than CASO Granules (technical anhydrous calcium chloride in granular form). Comparative performance tests and scientific research prove that it is the premier choice for ice melt. With its fast melting action and cold-temperature performance, CASO is easily distinguished from other ice melters because it: contains more than 90% calcium chloride, the most effective material for melting ice and snow melts ice 2 to 13 times faster than other ice melt materials absorbs moisture and generates heat to speed melting penetrates through ice 2 to 14 times faster than competing materials performs in a wider range of winter temperatures, even extreme cold
CASO Granules calcium chloride outperforms other ice formulations in all winter conditions (see graphs below)
CASO Granular - Ice penetration comparison (at -6C) 14 12 10 ratio of speed 8 (referred to 6 CaCl2) 4 2 0 14
1 CaCl2
2 NaCl
2 MgCl2
3 Urea
3 KCl CMA
CASO Granular - Melting speed comparison (at -6C) 14 12 10 ratio of speed 8 (referred to 6 CaCl2) 4 2 0 13
7 2 NaCl 3 MgCl2 3 Urea KCl CMA
1 CaCl2
While competing products stop working at -18C, CASO Granules keep working even when the temperature plummets to -32C, the lowest effective temperature of any ice melt product.
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CASO Flakes, dihydrate technical calcium chloride contains more than 75% calcium chloride. It is used by itself or mixed with rock salt and abrasives to give them extra power. Calcium chlorides highperformance properties make it superior to plain salt and other ice melting materials. CASO Flakes, works across a wider range of temperatures than other ice melting materials works much faster than rock salt alone melts ice faster and at lower temperatures than urea and potassium chloride melts ice faster than magnesium chloride, which means that more magnesium chloride, at added cost, is needed to match its performance
Hereinafter a graph which represents the performance comparison between CASO Flakes and other ice melt materials
CASO Flakes - Ice melt volume comparison (at -6C) 10 8 ratio of speed (referred to CaCl2) 6 4 2 0 1 CaCl2 1,24 MgCl2 1,3 NaCl 2 Urea KCl CMA 5
CASO Flakes, dihydrate technical calcium chloride provides additional benefits when it is mixed with other materials. It helps: make rock salt act faster and at lower temperatures keep abrasives like sand and cinders manageable and free flowing at cold temperatures imbed abrasive in ice to prevent them from being bounced off the surface by traffic whether used by itself, with rock salt, or with abrasive, CASO Flakes calcium chloride not only melts quicker, it also make it easier for you to mechanically remove snow and ice by penetrating and loosening it.
How to apply CASO calcium chloride Precautionary treatment of the roads (anti-icing) In wet situations (rain, fog, ) only rock salt is used (15-20 g/m2). On the contrary, in dry situation, rock salt has to be pre-wetted at 20-25% using a 27% CASO TEC Solution, keeping the same total quantity of salts on the surface (15-20 g/m2). The decision of not to use calcium chloride alone in the conditions described above, is for minimising the risk to generate hexahydrated crystals of CaCl2 (increasing the slippery of the surface), which could occur due to sudden and unpredictable climatic variations. In presence of permeable paving (porous), the total amount of salts to use has to be double (30-40 g/m2). De-icing treatment In presence of snow or ice, quantities of salts to be used are inclusive between 5 (min) and 25 (max) g/m2. CASO TEC LIQUID 27% is normally used both as a wetting agent of rock salt (NaCl) or directly spread on the road, it depends on by weather and temperature
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In presence of porous asphalt, a real risk that the liquid (water) trapped in the pores freezes, increasing its volume and forming a lot of points of compacted hard ice on the whole surface of the road increasing the risk of slipperiness (decreasing CAT Index, Transversal Adherence Coefficient) exists. In this case, only using calcium chloride, preferably in solid form to exploit its heat of dissolution, is possible to melt ice quickly, otherwise ice has to be removed mechanically using snow plough trucks (with blades). Risk of slippery As already described, the main risk on roads during winter season is their slipperiness in presence of rain, snow or ice. The use of melting agents permits to assure the circulation of vehicles even in case of snowfall or stormy weather, but in any case the adherence of the surfaces will decrease anyway with respect to the standard dry conditions. The following table contains values of CAT (transversal Adherence Coefficient) of roads in different conditions and in presence of different ice melters. Road condition Dry Soaked by rain (water) Soaked by rock salt solution Soaked by CaCl2 solution Soaked by CaCl2 solution in presence of crystals of CaCl2.6H2O Damage of concrete The freeze/thaw cycle poses the highest risk by far of damage for concrete during the winter months. To put this in sample terms, it is the build up of water [melted ice] being absorbed into the porous concrete, which then freezes and expands. This expansion within the concrete causes pressure to build up and eventually this build up will exceed the limit that the concrete was built to withstand. When the pressure becomes too much for the concrete to withstand, scaling generally occurs. The concrete absorbing the melted ice [water] is a fact of nature and cannot be blamed on the ice melter used. It can be likened to a sponge absorbing water. However, it should be noted that when an ice melter is used, more melted ice [water] will be produced, and therefore the potential of more water seeping into the concrete than if ice was left in its frozen state. As mentioned before, the freeze/thaw cycle is a natural process and there is no way of eliminating it. However to reduce the damage caused by this cycle, we strongly recommend that after applying the ice melter and when the ice turns into slush, that the slush be removed from the concrete pavement, sidewalk or driveway to reduce the amount of water that may penetrate the concrete thus reducing the pressure build up. Thanks to its lower freezing point, calcium chloride tends to re-freeze less quickly compared to other chlorides reducing the effective numbers of freeze/thaw cycles. Nevertheless, we recommend for not using ice melters on new concrete surfaces (less than one year old) or on poor quality concrete. Finally, damage to concrete is rarely caused by the ice melter used, but rather by the effects of the freeze/thaw cycle. The risk of damage can be reduced substantially by remembering these few points: Remove slush and broken ice. Use good ice melting products - prevent chemical damage - extend freeze/thaw cycle Try to prevent water build up on surface to reduce absorption. Ensure that concrete is of high quality construction to withstand your cold weather climate. Do not use ice melters on new, damaged, or unsealed concrete. CAT value 95-100% 60% 56% 54% 38%
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3.10 Anti-Dust treatment

During dry weather a breath of wind is all it needs to whip up thick clouds of dust on all nonmetalled surfaces used for traffic or for industrial or sporting activities. This dust is dirty, it gets in everywhere, and it irritates people and can even cause accidents as a result of poor visibility. When spread on the surface requiring treatment, CASO Calcium Chloride captures the ambient humidity in the air and turns into a solution that impregnates the ground and maintains sufficient humidity to keep the dust down as well as stopping the ground from drying out. Finally, the safety and healthiness of coal mines can be maintained as long as coal dust can be kept under control. Under certain conditions (high levels of coal dust on the ground or in the air), the risk of explosion is high. What's more, dust present in the air causes silicosis, a disease typical in coal miners. Using CASO Calcium Chloride can significantly improve safety and working conditions. Unpaved surfaces treatment CASO calcium chloride scattered on the surface to be treated, picks up moisture from the air (hygroscopicity), and turns into a solution (deliquescence) going to soak the soil. This solution maintains the soil lightly humidified, enough to fix the dust, avoiding soil drying and also inhibiting the formation of new dust. The use of CaCl2 has also the effect to improve the consolidation and stabilization of the treated surfaces, giving them both a better uniformity and elasticity (this will decrease the effort of the users of playgrounds) thanks to its ability to increase the surface tension of water that covers as a film each small parts of the soil itself, and to enhance its resistance to frost (especially the freeze-thaw alternations) characteristic of the winter period due to its property of lowering the freezing point of water. The absorption of air humidity by a CaCl2 solution will continue, at specified temperature, until the concentration of salt in the solution reaches a specified value (equilibrium) where the absorption of atmospheric humidity is offset by the evaporation of moisture of soil, depending on whether the relative humidity is above or below the corresponding equilibrium value. The tables below show CASO characteristics of its behaviour towards hot (relative humidity balance) and cold temperatures (freezing point)

External Temperature, C 10 20 30 40 50 60 Starting of crystallization of solution, C -6 -12 -20 -33 -50
Relative Humidity balance, % 40.3 34.6 21.6 19.0 16.8 17.2 CaCl2 concentration, % 10 15 20 25 30
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CASO calcium chloride in solid or liquid form, can be used as dust suppressant agent for unpaved roads, mine haul, logging and other type of industrial roads, truck terminals and parking lots, shoulders, railroad yards, construction sites and other unpaved surfaces, campsites, tennis courts, riding schools,
How to apply CASO calcium chloride CASO calcium chloride has to be applied at least in two steps: first application has to be done in late spring, but additional treatment should be done after 4-5 weeks in case of very dry weather conditions; a second application has to be done in late summer and it will help protect the road from frost during winter. Normally, this operation requires 1/2 or 1/3 of initial dosage. It is recommended not to apply the product during or just before a heavy rainfall. If applied just before, the material may wash away. CASO works better if it is applied to a wet road. Application to a dry surface makes a relevant difference in how much less effective the solution works for dust control. If possible, apply CASO after a light rain so materials are moister and more workable. In case of dry weather conditions, and in presence of minimal moisture of surface, it is recommended to apply the product at the end of the day or early in the morning, when the humidity is higher, and to soak the soil in advance in case the application should necessarily be made during the daylight hours. Be careful about applying CASO when the outside temperature is below 4C. In this case a proper concentration of CaCl2 has to be chosen to avoid that a high concentration of applied solution makes the road surface extremely slippery. Regular CASO TEC liquid 36% has to be used in this condition. Restrict the use of CASO calcium chloride, as well as other chloride-based dust suppressant, within 8 meters of a body of water. In areas of swallow groundwater, determine if significant migration of the chloride would reach the groundwater table. Restrict the use of chlorides if low salt tolerant vegetation is within 8 meter of the treated area. Typical low-tolerant vegetation includes various varieties of alder, hemlock, larch, maple, ornamentals and pine. Use of solid CASO calcium chloride for small surfaces is preferable. The bags are easy to store and the product requires less specialized equipment to apply. CASO Liquid, being easier to handle and to apply, is best for larger applications. Quantities to apply Product CASO FLAKES CASO GRANULS Dosage 0.9 kg/m 0.7 kg/m
2 2
CASO LIQUID 36%
1.7 l/m
2
Pros Attracts moisture on the air and retains it on surface. Lowers freezing point of water minimizing frost heave and reducing freeze-thaw cycles. Increases compacted density of road material. Effectiveness retained after reblading.
Cons Slightly corrosive to metal, highly to aluminium and its alloys. Rainwater tends to leach out product easily (as a consequence it has to be re-applied costs increasing) If high fines content in treated material, the surface may become slippery when wet.
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SAFETY & ENVIRONMENT
Safety & Environment have to be taken seriously. They are as important for you as they are for us. We make it a point of honour to keep you well informed. EU Regulation 1272/2008 as amended, repealing EU Directive 67/548/EEC, sets out classification and labelling criteria for hazardous substances and mixtures. It also established a list of substances with their harmonized classifications and labelling elements at Community level. In that context, calcium chloride fulfils the criteria for classification as substance irritant to eyes. Calcium chloride is assigned the hazard statement H318 for anhydrous product and H319 for other hydrated forms or for solutions. Code H319 - Warning Code H318 - Danger
Products concerned: dihydrate and liquid CaCl2
Products concerned: anhydrous CaCl2
CASO calcium chloride has been registered according to the REACH Regulation (EC) N 1907/2006 by Solvay Chimica Italia SpA under the tonnage band above 1000 t/y with the Registration Number 01-2119494219-28. Since calcium chloride is classed as an 'irritant', it is necessary to observe certain elementary precautions. These include: never place the skin in prolonged contact with CASO or any of its solutions, use water, preferably lukewarm, to thoroughly rinse any part of the body affected by this product, wear gloves made from rubber or plastic, avoid any inhalation of CASO dust, wear protective glasses when handling CASO, avoid working with equipment made from leather. With regard to the effects of CASO on the environment, we offer you the following thoughts: Calcium and chlorine ions are everywhere in the atmosphere and are used physiologically for living organisms. They occur naturally in the soil, rocks and sediment, as well as in surface or deep water. Calcium is an essential element in the cycle of life. It plays a part in the mineral balance of plants and is an important element in the composition of the water in our rivers and in our mains supplies. The effects on the environment of calcium in the form of calcium chloride are not to be feared. Chlorine ions, the other component of CASO, should be looked at from two points of view. On the whole, the chlorine found in river water rarely exceeds the levels allowed by official bodies responsible for public health and the environment. Certain periods of the winter have revealed very short peaks in concentration. Recent studies have shown that these occurrences do not have an important influence on the aquatic environment. As far as fluoride is concerned, even in those areas where CASO is used intensively do we not find anything like the destruction of plants put forward by certain alarmists. The occasional accelerated fall of leaves or plant thorns (biological regulators of the latter) have been observed, as has the appearance of plants which are particularly resistant to chloride or the mutation of certain species of plant.
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In 45 years of spreading CASO on our roads, no serious incident concerning an animal ingesting this product has been brought to our attention. For more detailed information, please to look at CASO Safety Data Sheets
LOGISTICS
5.1 Packaging
Each grade of the product is identified by different coloured marking on the bags: CASO Technical grade (TEC, black) CASO FCC grade (FCC, blue), Food Additive INS509 (for extra-EU countries ONLY) CASO Feed grade (FEED, green) CASO FOOD grade (FOOD, red), Food Additive E509 (for EU countries ONLY)
According to the product grade and the production unit, CASO calcium chloride can be supplied: In bulk, full load of 25-30 tons with pneumatic unloading systems In 875 or 1.000 kg bulk bags In 25 kg polypropylene single bag on 875, 1.000 or 1.250 kg pallets Packaging specifications are available for each type of packaging. For more detailed information, please contact Solvays sales department
Handling and Storage
Although CASO calcium chloride is not subject to expiry, the experience about the decay of its main chemical-physical properties, mainly because of its hygroscopicity, advises a preferable use in a twenty-four months period. In order to check the good conservation state, it is advised to control, at least every six months, the products calcium chloride content, as well as to verify any possible presence of agglomerates (it would mean that a humidity absorption from the environment occurred). CASO, dihydrate flakes and powder or anhydrous granules of calcium chloride, may be stored, in bulk, in steel equipment, provided that entry of moisture is minimized. Corrosion problems may become severe on steel equipment where calcium chloride deliquesces due to moisture pick-up and air is present. For extended service in such circumstances, resistant materials in lieu of iron or steel are recommended. CASO is also shipped in watertight bags or bulk-bags on wood pallets wrapped with plastic film (only for bags); it can be stored outside, although preferably under a tarpaulin or shelter. Calcium chloride solutions may be stored in steel equipment with or without corrosion inhibitors.
6.1 Dry calcium chloride storage bins

Most common construction-grade steel materials are suitable for calcium chloride bins as well as auxiliary equipment including valves, chutes, vents, piping, and so on. Care should be taken to make all such equipment moisture-tight. Venting should be limited to the duration only of filling and discharging calcium chloride from the equipment. This minimizes accumulation of atmospheric moisture, which will otherwise increase the corrosion rate of the steel, reduce the assay of the product, and lead to product caking. Lining of steel equipment with resistant paints or synthetic coatings (polymerized epoxies or vinyl ester resins) is recommended if special corrosion problems or product quality requirements exist. Bin foundations must meet local soil bearing conditions and codes.
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The hopper should be designed with relatively steep sides, at least a 45 slope for flakes and granules and 75 slope for powder calcium chloride, to assure flow to the feeding device without sticking or clogging. Hoppers may be constructed of steel and should have tight fitting covers. Powder calcium chloride absorbs moisture very rapidly and usually requires some form of agitation or mechanical appliance to induce a regular and steady flow. This may be accomplished by a mechanical agitator, a flexing hopper, or a vibrator system attached to the hopper.
6.2 Dry calcium chloride conveyors and elevators

Belt, screw and drag conveyors plus elevators are in common service for unloading bulk hopper cars into storage bins. Additionally, pneumatic conveying methods are used to transfer flakes calcium chloride to storage either from bulk hopper cars or from bulk pneumatic transports. Some plastic and rubber components are used in such equipment, but the major components are usually steel or sometimes aluminium. These metals must be washed with water and dried thoroughly immediately after use to reduce corrosion rates. Remark: because the product crashes during the manipulation, before choosing the adequate unloading and/or movement system to be used, well evaluate which limit value of degradation of the product is admitted.
6.3 Storage tanks for liquid calcium chloride

For many customers, storage tanks holding 50 or 80 cubic meters are of suitable capacity. This depends, of course, on the rate of consumption and the reverse supply required for use until more calcium chloride is received. The normal rule of thumb in determining storage capacity is 1.5 times the anticipated delivery volume. Either horizontal or vertical cylindrical tanks are satisfactory for storage of calcium chloride solutions. Steel storage tanks should be constructed of mild steel (preferably lined) with all-welded construction. Polyester fibreglass storage tanks offer excellent corrosion resistance and can be used in place of mild steel except where temperatures of calcium chloride exceed 90 C. The storage tank should be provided with required pipe connections to receive the tank car contents through the top of the tank and to draw off the liquid at a point a few centimetres above the bottom. Also, a drain connection should be located at the lowest point of the tank to permit flushing when necessary. A 24-inches diameter access manhole should be provided in the top of the tank along with a vent to the atmosphere. The tank foundations must meet local soil bearing conditions and codes, and a secondary containment basin should be provided.
6.4 Dissolving CASO

Solid calcium chloride can be transferred by storage silo or directly by hopper car or truck to a dissolving and storage tank. IMPORTANT: an extreme rise in temperature accompanies dissolving of calcium chloride in water. Hot solutions may cause thermal burns; care should be exercised to avoid contact. For complete information, see the Material Safety Data Sheet.
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How to prepare a calcium chloride solution from solid product Supposing to want to prepare a 30% calcium chloride solution, having a storage tank from 10.000 l of capacity, starting to solid product CASO Flakes at 78% of calcium chloride, it will be possible to calculate the quantity of the water needed to dissolve a calculated quantity of CASO Flakes. So: Density of 30% calcium chloride solution (at 20 C): 1,283 kg/dm Filling coefficient of storage tank: 90% The quantity of solution we can prepare will be: 1,283 x 10.000 x 90% = 11.457 kg The quantity of CASO Flakes to be dissolved to obtain the 30% solution will be: 30% x 11.547 : 78% = 4.441 kg
The quantity of water to dissolve 4.441 kg of CASO Flakes 78% will be: 3
11.457 4.441 = 7.106 kg After the calculation, fill the container with two-thirds of total quantity of water necessary to obtain the final solution; then add the solid product gradually stirring carefully with a mechanical agitator or with air as appropriate. When the solid product has completely dissolved, the balance of the water is added to fill the container with the rest of water necessary (one-third) and then agitated slowly until a uniform concentration is obtained. In making up calcium chloride solutions, the calcium chloride should be added to the water. Do not add calcium chloride into the container and then add water since the calcium chloride may form a solidified mass which is difficult to dissolve completely. When a solid CASO is used to prepare a solution, two tanks are usually required, the solution being prepared in one tank while the other is discharging through the feeding appliance. If a clear solution is required, a decantation or filtration system is necessary.
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Chemical-physical properties of CASO calcium chloride
Much of the data concerning the properties of calcium chloride have been assembled from published literature which often pertains to pure product. As the commercial product contains sodium chloride and minor quantities of certain other ingredients, some of the data may not apply strictly to the commercial product. However, in general, the data of pure calcium chloride may be used for most commercial applications. Data relating specifically to the commercial product will be so indicated.
7.1 Properties of Anhydrous calcium chloride

Molecular weight (CaCl2): Specific gravity 110.99
This ratio of the weight of a volume of pure anhydrous calcium chloride to an equal volume of water @ 4C, which is interest principally in the laboratory, should not be confused with bulk density which is the actual weight of a unit volume of any product and is of practical value in bulk handling and storage. Specific gravity: Melting point: Specific heat @ 61C: Latent heat of fusion @ 772C: Heat of formation @ 18C: Heat of solution @ 18C in 400 moles of water: Coefficient of expansion: Boiling point: @ 20/4C: 2.26 @ 15/4C: 2.152 772C 0.164 cal/g/C 54.2 cal/g -7.190 kJ/kg -680 kJ/kg 0.00062 above 1600C
7.2 Properties of the hydrates of calcium chloride

The four known hydrates of calcium chloride with available pertinent data are: Calcium chloride monohydrate (CaCl2.H2O) Composition Molecular weight Melting point Heat of formation @ 18C: Heat of solution @ 18C in 300 moles of water: Calcium chloride dihydrate (CaCl2.2H2O) Composition Molecular weight Melting point Heat of formation @ 18C: Heat of solution @ 18C in 400 moles of water: Calcium chloride tetrahydrate (CaCl2.4H2O) Composition Molecular weight Melting point Heat of formation @ 18C: Heat of solution @ 18C in 400 moles of water: 60.6% CaCl2 39.4% H2O 183.05 45.3C -10.980 kJ/kg -50 kJ/kg 75.5% CaCl2 24.5% H2O 147.03 175.5C -9.490 kJ/kg -290 kJ/kg 86.0% CaCl2 14.0% H2O 129.01 260C -8.610 kJ/kg -380 kJ/kg
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Calcium chloride hexahydrate (CaCl2.6H2O) Composition Molecular weight Melting point Specific heat @ 0C Latent heat of fusion @ 29.92C Heat of formation @ 18C: Heat of solution @ 18C in 400 moles of water: 50.7% CaCl2 49.3% H2O 219.09 29.92C 0.320 cal/g/C 40.7 cal/g -11.911 kJ/kg 80 kJ/kg
7.3 Properties of calcium chloride solutions

Densities, concentrations and crystallizing temperatures Table 1 contains data obtained in the laboratory with solutions prepared by dissolving flakes 78% CaCl2 and 1.5% of NaCl. Data applies to concentrations up to 45% CaCl2 but specific gravities are limited to 1.410, above which crystals appear at the standard temperature. Temperature at which crystals appear are shown in column 3. Table 2 gives the corrections which must be applied to convert densimeter readings to specific gravity @ 15.6C, when observations are taken at temperatures other than 15.6C, using a standard specific gravity densimeter calibrated @ 15.6C. Table 3 shows the relation between percent calcium chloride and densimeter readings at various temperature obtained with a standard specific gravity densimeter calibrated @ 15.6C. Highly concentrated calcium chloride solutions Data for concentrations above 40% CaCl2 are not included in Table 1 for the reason that solutions containing above 40.8% CaCl2 have suspended crystals or are solidified at or above 15.6C; therefore densimeter readings at 15.6C are either unreliable or unobtainable. Densimeter readings at various temperatures for concentrations to 45% CaCl2 are shown in Table 3. Table 4 gives densities at various temperatures and crystallization temperatures for concentrations between 50% and 72% CaCl2. Although solutions from 29.8% to 50% CaCl2 do not actually freeze solid until a temperature of -55C is reached, they appear solid at considerably higher temperatures, due to the great volume of CaCl2.6H2O crystals.
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Table 1 - Densities, Concentrations and crystallizing temperatures of calcium chloride solutions
(1)specific (2)% CaCl2 gravity @15,6C actual w/w 1,000 1,009 1,018 1,026 1,034 1,043 1,052 1,060 1,069 1,078 1,087 1,096 1,105 1,115 1,125 1,135 1,145 1,155 1,165 1,175 1,186 1,195 1,206 1,218 1,228 1,239 1,250 1,260 1,272 1,283 1,290 1,295 1,306 1,317 1,328 1,340 1,351 1,363 1,374 1,386 1,398 1,410 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0 11,0 12,0 13,0 14,0 15,0 16,0 17,0 18,0 19,0 20,0 21,0 22,0 23,0 24,0 25,0 26,0 27,0 28,0 29,0 29,6 30,0 31,0 32,0 33,0 34,0 35,0 36,0 37,0 38,0 39,0 40,0 41,0 42,0 43,0 44,0 45,0 -
(3)Crystallization starts C 0,5 0,9 1,4 1,9 2,4 2,9 3,4 4,1 4,7 5,4 6,2 7,1 8,0 9,2 10,3 11,6 13,0 14,5 16,2 18,0 19,9 22,1 24,4 26,8 29,4 32,1 35,1 38,8 45,2 51,0 46,0 36,2 28,6 21,6 15,4 9,8 4,4 0,8 5,6 9,8 13,3 16,4 18,8 21,0 22,8 24,2
(4)kg of Flakes (5)kg of Granuls 78% per l of 94% per l of water water 0,012 0,012 0,026 0,023 0,040 0,034 0,054 0,044 0,068 0,056 0,084 0,069 0,098 0,080 0,114 0,093 0,131 0,106 0,146 0,118 0,164 0,132 0,181 0,145 0,200 0,159 0,219 0,175 0,238 0,190 0,259 0,207 0,279 0,223 0,300 0,240 0,321 0,255 0,344 0,273 0,369 0,288 0,393 0,305 0,419 0,326 0,445 0,342 0,471 0,361 0,501 0,382 0,530 0,403 0,561 0,423 0,592 0,444 0,611 0,459 0,627 0,469 0,660 0,491 0,694 0,514 0,732 0,540 0,773 0,566 0,812 0,593 0,856 0,626 0,904 0,647 0,950 0,677 1,001 0,710 1,053 0,740 At concentration above 40,8% CaCl2 solutions contain suspended crystals @ 15,6C.
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Table 2 - Temperature correction for density of calcium chloride solution

specific Corrections to be applied to density of calcium chloride solutions at various temperatures, using a gravity densimeter calibrated @ 15.6C. reading -17,8C -12,2C -6,7C -1,1C +4,4C +10C +15,6C +21,1C +26,7C +32,2C +37,8C 1,000 0,002 0,001 0,001 0,002 0,004 0,005 1,010 0,002 0,001 0,001 0,002 0,004 0,005 1,020 0,002 0,001 0,001 0,002 0,004 0,006 1,030 0,003 0,002 0,001 0,001 0,002 0,004 0,006 1,040 0,003 0,002 0,001 0,001 0,002 0,004 0,006 1,050 0,004 0,003 0,001 0,001 0,003 0,004 0,006 1,060 0,004 0,003 0,001 0,001 0,003 0,005 0,007 1,070 0,004 0,003 0,002 0,001 0,003 0,005 0,007 1,080 0,004 0,003 0,002 0,001 0,003 0,005 0,007 1,090 0,005 0,003 0,002 0,001 0,003 0,005 0,007 1,100 0,005 0,003 0,002 0,001 0,003 0,005 0,007 1,110 0,006 0,005 0,004 0,002 0,001 0,003 0,005 0,007 1,120 0,006 0,005 0,004 0,002 0,002 0,003 0,006 0,008 1,130 0,006 0,005 0,004 0,002 0,002 0,004 0,006 0,008 1,140 0,007 0,006 0,004 0,002 0,002 0,004 0,006 0,008 1,150 0,007 0,006 0,004 0,002 0,002 0,004 0,006 0,008 1,160 0,009 0,007 0,006 0,004 0,002 0,002 0,004 0,006 0,009 1,170 0,009 0,008 0,006 0,004 0,002 0,002 0,004 0,006 0,009 1,180 0,010 0,008 0,006 0,004 0,002 0,002 0,004 0,007 0,009 1,190 0,010 0,008 0,007 0,005 0,003 0,002 0,004 0,007 0,009 1,200 0,011 0,010 0,009 0,007 0,005 0,003 0,002 0,004 0,007 0,009 1,210 0,012 0,011 0,009 0,007 0,005 0,003 0,002 0,005 0,007 0,010 1,220 0,012 0,011 0,009 0,007 0,005 0,003 0,002 0,005 0,007 0,010 1,230 0,013 0,011 0,009 0,007 0,005 0,003 0,002 0,005 0,007 0,010 1,240 0,013 0,011 0,009 0,007 0,005 0,003 0,003 0,005 0,008 0,010 1,250 0,013 0,012 0,010 0,008 0,005 0,003 0,003 0,005 0,008 0,010 1,260 0,014 0,012 0,010 0,008 0,005 0,003 0,003 0,005 0,008 0,011 1,270 0,014 0,012 0,010 0,008 0,005 0,003 0,003 0,005 0,008 0,011 1,280 0,015 0,013 0,010 0,008 0,006 0,003 0,003 0,005 0,008 0,011 1,290 0,015 0,013 0,011 0,008 0,006 0,003 0,003 0,006 0,008 0,011 1,300 0,015 0,013 0,011 0,008 0,006 0,003 0,003 0,006 0,009 0,011 1,310 0,016 0,014 0,011 0,009 0,006 0,003 0,003 0,006 0,009 0,012 1,320 0,016 0,014 0,011 0,009 0,006 0,003 0,003 0,006 0,009 0,012 1,330 0,017 0,014 0,012 0,009 0,006 0,003 0,003 0,006 0,009 0,012 1,340 0,017 0,015 0,012 0,009 0,006 0,003 0,003 0,006 0,009 0,012 1,350 0,018 0,015 0,012 0,009 0,006 0,003 0,003 0,006 0,009 0,012 1,360 0,013 0,009 0,006 0,004 0,003 0,006 0,010 0,013 1,370 0,010 0,007 0,004 0,003 0,006 0,010 0,013 1,380 0,007 0,004 0,003 0,007 0,010 0,013 1,390 0,004 0,004 0,007 0,010 0,013 1,400 0,004 0,004 0,007 0,010 0,013 1,410 0,004 0,007
Temperatures below 15.6C: observed densimeter reading minus Temperature correction = Specific Gravity @ 15.6C. Temperatures above 15.6C: observed densimeter reading plus Temperature correction = Specific Gravity @ 15.6C.
No corrections
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Table 3 - Solution concentrations at other than 15.6C Densimeter readings of calcium chloride solutions at various temperatures, using a densimeter calibrated @ 15.6C % CaCl2 -17,8C -12,2C -6,7C -1,1C +4,4C +10C +15,6C +21,1C +26,7C +32,2C +37,8C 1,002 1,001 1,000 0,999 0,998 0,996 0,995 2 1,020 1,019 1,018 1,017 1,016 1,014 1,012 4 1,037 1,036 1,035 1,034 1,033 1,032 1,030 1,028 6 1,056 1,055 1,053 1,052 1,051 1,049 1,048 1,046 8 1,073 1,072 1,071 1,069 1,068 1,066 1,064 1,062 10 1,092 1,090 1,089 1,087 1,086 1,084 1,082 1,080 11 1,101 1,099 1,098 1,096 1,095 1,093 1,091 1,089 12 1,111 1,110 1,109 1,107 1,105 1,103 1,102 1,100 1,097 13 1,121 1,120 1,119 1,117 1,115 1,113 1,112 1,110 1,107 14 1,131 1,130 1,129 1,127 1,125 1,123 1,122 1,119 1,117 15 1,142 1,141 1,139 1,137 1,135 1,133 1,131 1,129 1,127 16 1,152 1,151 1,149 1,147 1,145 1,143 1,141 1,139 1,137 17 1,164 1,162 1,161 1,159 1,157 1,155 1,153 1,151 1,149 1,147 18 1,174 1,173 1,171 1,169 1,167 1,165 1,163 1,161 1,159 1,156 19 1,185 1,183 1,181 1,179 1,177 1,175 1,173 1,171 1,169 1,166 20 1,197 1,196 1,194 1,193 1,191 1,189 1,186 1,184 1,182 1,179 1,177 21 1,207 1,206 1,204 1,202 1,200 1,198 1,195 1,193 1,191 1,188 1,186 22 1,218 1,217 1,215 1,213 1,211 1,209 1,206 1,204 1,202 1,199 1,197 23 1,231 1,229 1,227 1,225 1,223 1,221 1,218 1,216 1,213 1,211 1,208 24 1,241 1,239 1,237 1,235 1,233 1,231 1,228 1,226 1,223 1,221 1,218 25 1,252 1,251 1,249 1,247 1,244 1,242 1,239 1,236 1,234 1,232 1,229 26 1,264 1,262 1,260 1,258 1,255 1,253 1,250 1,247 1,245 1,242 1,240 27 1,274 1,272 1,270 1,268 1,265 1,263 1,260 1,257 1,255 1,252 1,250 28 1,287 1,285 1,282 1,280 1,278 1,275 1,272 1,269 1,267 1,264 1,261 29 1,298 1,296 1,294 1,291 1,289 1,286 1,283 1,280 1,278 1,275 1,272 30 1,311 1,309 1,306 1,303 1,301 1,298 1,295 1,292 1,289 1,287 1,284 31 1,322 1,320 1,317 1,315 1,312 1,309 1,306 1,303 1,300 1,297 1,295 32 1,334 1,331 1,329 1,326 1,323 1,320 1,317 1,314 1,311 1,308 1,305 33 1,346 1,343 1,340 1,337 1,334 1,331 1,328 1,325 1,322 1,319 1,316 34 1,355 1,352 1,349 1,346 1,343 1,340 1,337 1,334 1,331 1,328 35 1,364 1,360 1,357 1,354 1,351 1,348 1,345 1,342 1,339 36 1,373 1,370 1,367 1,363 1,360 1,357 1,354 1,351 37 1,381 1,378 1,374 1,371 1,368 1,364 1,361 38 1,390 1,386 1,383 1,379 1,376 1,373 39 1,402 1,398 1,394 1,391 1,388 1,385 40 1,410 1,406 1,403 1,400 1,397 41 1,420 1,416 1,412 1,408 42 1,433 1,429 1,424 1,420 43 1,446 1,441 1,436 1,431 44 1,453 1,448 1,444 45 1,465 1,459 1,454
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Table 4 - Crystallization and densities at various temperatures for concentrations between 50% and 72% CaCl2
CaCl2 hydrate crystals appear at 29,700 36,000 41,000 44,600 63,500 85,500 108,000 125,500 143,500 155,500 164,500 170,000 Approximate weight in kgs of a liter of solution at various temperatures Freezed solid at 55,0 29,8 29,8 29,8 29,8 29,8 45,3 45,3 45,3 45,3 45,3 45,3 37,8C 48,9C 65,6C 100C 115,6C 137,8C 160C 1,51 1,53 1,50 1,52 1,55 1,57 1,49 1,51 1,53 1,56 1,58 1,46 1,49 1,51 1,53 1,55 1,57 176,7C
%CaCl2 50 52 54 56 58 60 62 64 66 68 70 72
1,51 1,53 1,57 1,59
1,50 1,51 1,56 1,58 1,61
1,50 1,55 1,57 1,61 1,63 1,67
1,56 1,59 1,62 1,65 1,69 1,71
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7.4 Solubility
Although calcium chloride dissolves readily in water to form solutions of high concentrations, due account must be taken of the temperature at which solid hydrates separate out of these solutions. A detailed diagram of the solid and liquid phases showing the temperature and concentration reactions of pure calcium chloride (CaCl2) and water is given in Figure 1. The irregular line in this diagram is the solubility or saturation curve of calcium chloride in water. The area above the curve is the region of unsaturated solution within which calcium chloride is completely soluble. Below the line, the saturated solution contains suspended particles of ice, or of hydrates of calcium chloride, or is a completely solidified mass of hydrates. The lettered areas, as explained in the table below, denote temperatures and concentrations within which the various hydrates of their mixtures with saturated solutions can exist.
% CaCl2 Area A B C D E F G H I J CaCl2.2H2O CaCl2.4H2O CaCl2.6H2O Saturation curve for from ICE 0 0 29,8 50,7 50,3 60,6 56,6 75,5 to 29,8 50,7 50,7 60,6 60,6 75,5 75,5 86 175,5 74,9 NONE 45,3 45,3 175,5 56,6 NONE 86 29,8 29,8 45,3 50,3 NONE 74,9 -55 -55 29,8 29,8 NONE 56,6 Temperature C at end below from 0 to -55 Liquid phase contains % Solid phases CaCl2 from 0 NONE 50,3 to 29,8 ICE ICE CaCl2.6H2O CaCl2.6H2O CaCl2.6H2O CaCl2.4H2O CaCl2.4H2O CaCl2.4H2O CaCl2.2H2O CaCl2.2H2O CaCl2.2H2O CaCl2.H2O Solid phase transition at % CaCl2 C
29,8
-55
50,3
29,8
56,6
45,3
74,9
175,5
CaCl2.H2O 74,9 86 175,5 260 Area above saturation curve. Unsaturated solutions
Referring to the solubility diagram, when a solution containing 21.5% CaCl2 is cooled to about -21.1C, crystals of ice begin to form, and the concentration of the remaining solution increases. As the temperature is lowered further, these ice crystals continue to form and the mixture of crystals, and solution forms a gradually thickening slush. With continued cooling to about -55C, the concentration of the remaining solution finally reaches the lowest point of the curve (29.8% CaCl2), and the mixture becomes completely solid, consisting of calcium chloride hexahydrate (CaCl2.6H2O) and ice. The same is true for solutions containing 29.8% to 50.7% CaCl2 except that crystals of calcium chloride hexahydrate are formed on cooling instead of ice crystals. Upon warming, the changes occur in the reverse order until the clear, unsaturated solution is restored. As another example of the application of this solubility diagram, when a calcium chloride solution containing 55% CaCl2 is cooled from a higher temperature, it becomes saturated at +42.8C. Further lowering of the temperature, following the 55% line downward into the area E, causes the tetrahydrate (CaCl2.4H2O) to separate. The suspension becomes gradually thicker until at +29.8C, the liquid portion, then being a 50.3% CaCl2 solution, solidifies completely in area D to produce a mixture of CaCl2.4H2O and CaCl2.6H2O, and no further change occurs with continued decrease in temperature.
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As indicated on the diagram, these data were obtained with pure calcium chloride. The saturation curve and freezing points with solutions up to a concentration of 29.8% CaCl2, are practically the same as for pure solutions; above 29,8% the curve follows the same general pattern (and direction) but falls slightly to the left of the curve for pure calcium chloride. The difference is slight between 29,8% and 50% CaCl2 but increases somewhat at higher concentrations. The effect of a small percentage of sodium chloride and other minor soluble impurities is to raise the saturation temperature slightly for any given concentration of CaCl2. Thus, a 40% CaCl2 solution becomes saturated when cooled down to approximately 13C from a higher temperature, whereas a pure 40% solution is saturated at approximately 12C. Figure 1 - Solubility of pure calcium chloride in water- Freezing point diagram
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7.5 Apparent solidification vs. actual freezing temperatures

Figure 2, is an enlarged portion of the saturation curve of Figure 1 below 45% concentration. The data for the solid line were obtained in our laboratory with solutions of commercial calcium chloride. This line represent the temperatures at which crystals first appear upon cooling and not that at which freezing to a solid mass occurs. The freezing point of water may be reduced by the addition of calcium chloride. At a concentration of 29,8% CaCl2, no ice crystals will form until a temperature of approximately -55C is reached. When a solution containing less than 29,8% CaCl2 is gradually cooled, crystals of ice appear as the saturation curve of ice is intersected. Upon further lowering of temperature, more ice will form, and the liquid portion will increase in CaCl2 content. Eventually the mass will be a thick slush and may even appear solid, although complete solidification will not occur until the freezing point temperature of -55C is reached. The dotted line curve, Figure 2, traces the apparent solidification temperatures. Figure 2 - Ice saturation and apparent solidification of commercial calcium chloride solutions
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7.6 Boiling temperatures

Figure 3 below gives the boiling points of pure calcium chloride solutions between 0 and 60% CaCl2 according to Baker and Waite (Chemical & Metallurgical Engineering, 25, (1921) 1174). The boiling points of solutions of the commercial product follow the same curve to approximately 25%, then gradually increase to one degree Celsius higher at 40%, approximately two degrees higher at 55%, and approximately three degrees higher above 65% CaCl2 due to impurities. Figure 3 - Boiling temperatures of calcium chloride solutions
145 140 135 temperature C 130 125 120 115 110 105 100 0 5 10 15 20 25 30 35 40 45 50 55 60 % w/w calcium chloride
7.7 Vapor pressure

Vapor pressure in mmHg (millimeters of mercury) existing over the hydrates and water solutions of calcium chloride are shown in Figure 4, at temperature from 0 to 80C. Table 5 shows the vapor pressure of saturated calcium chloride solutions compared to pure water and the related values of Relative Humidity of the air below at which calcium chloride becomes deliquescent. Table 6 shows the vapor pressure for cold CaCl2 diluted solutions. Vapor pressure data are useful for explaining the moisture absorption properties of calcium chloride and for determining its effectiveness in the dehumidification of air or other gases.
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Figure 4 - Vapor pressure over CaCl2 solutions

vapour pressure @ 0C in mbar vapour pressure @ 40C in mbar vapour pressure @ 20C in mbar vapour pressure @ 80C in mbar
100 90
vapour pressure @ 0, 20 and 40C - mbar
500 450 400 350 300 250 200 150 100 50 0 0 5 10 15 20 25

% w/w CaCl2 vapour pressure @ 80C - mbar
80 70 60 50 40 30 20 10 0 30 35 40 45 50
Table 5 - Vapor pressures compared of pure water and saturated CaCl2 solutions.
Vapor pressure pure water in mmHg 4,6 6,5 9,2 12,8 17,5 23,8 31,7 42,2 55,3 74,5 92,5 149,5
5,0 10,0 15,0 20,0 25,0 29,9 35,0 40,0 45,3 50,0 60,0
Vapor Air pressure saturated Relative Humidity CaCl2 % solutions in mmHg 2,1 45,6 2,8 41,8 3,7 40,3 4,8 37,2 6,1 34,8 7,0 30,2 6,9 21,6 8,6 20,8 10,5 19,0 12,1 16,8 15,5 17,2 25,7 17,4
Among 25 and 29,9C vapor pressure value reaches a maximum of 7,36 mmHg at 28,5C. Example: at 15C and Air Relative Humidity equal or above 37.2%, calcium chloride is deliquescent: it absorbs humidity.
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Table 6 - Vapor pressure for cold CaCl2 solutions (diluted)

CaCl2 Specific Freezing Gravity @ g/100 g of g/ 100 g of point C +6C 15C (kg/l) solution water Vapor pressure at different temperatures (mmHg) +4C +2C 0C -2C -4C -6C 2,76 -8C 2,32 -10C 1,95 -12C 1,63 -14C 1,36 -16C 1,13 -18C -20C 0,94 0,77
1,00 7,01 6,10 5,29 4,58 3,88 3,28 1,01 1,3 1,3 0,6 6,97 6,07 5,26 4,56 1,02 2,5 2,6 1,2 6,93 6,03 5,23 4,53 1,03 3,6 3,7 1,8 6,90 6,00 5,20 4,50 1,04 4,8 5,0 2,4 6,86 5,96 5,17 4,48 3,86 1,05 5,9 6,3 3,0 6,81 5,92 5,13 4,45 3,83 1,06 7,1 7,6 3,7 6,76 5,88 5,10 4,42 3,81 1,07 8,3 9,0 4,4 6,71 5,84 5,06 4,38 3,78 3,26 1,08 9,4 10,4 5,2 6,66 5,79 5,02 4,35 3,75 3,23 1,09 10,5 11,7 6,1 6,60 5,74 4,98 4,31 3,72 3,21 1,10 11,5 13,0 7,1 6,55 5,70 4,95 4,28 3,69 3,18 1,11 12,6 14,4 8,1 6,49 5,65 4,90 4,24 3,66 3,15 1,12 13,7 15,9 9,1 6,41 5,58 4,84 4,19 3,61 3,11 1,13 14,7 17,3 10,2 6,36 5,53 4,80 4,15 3,58 3,09 1,14 15,8 18,8 11,4 6,28 5,46 4,74 4,10 3,54 3,05 1,15 16,8 20,2 12,7 6,20 5,40 4,68 4,05 3,49 3,01 1,16 17,8 21,7 14,2 6,13 5,33 4,62 4,00 3,45 2,97 1,17 18,9 23,3 15,7 6,03 5,25 4,55 3,94 3,40 2,93 1,18 19,9 24,9 17,4 5,93 5,16 4,47 3,87 3,34 2,88 1,19 20,9 26,5 19,2 5,83 5,07 4,40 3,81 3,29 2,83 1,20 21,9 28,0 21,2 5,71 4,97 4,31 3,73 3,22 2,77 1,21 22,8 29,6 23,3 5,59 4,87 4,22 3,65 3,15 2,72 1,22 23,8 31,2 25,7 5,47 4,76 4,12 3,57 3,08 2,65 1,23 24,7 32,9 28,3 5,30 4,61 4,00 3,46 2,99 2,57 1,24 25,7 34,6 31,2 5,15 4,48 3,88 3,36 2,90 2,50 1,25 26,6 36,2 34,6 4,98 4,33 3,75 3,25 2,80 2,42 1,26 27,5 37,9 38,6 4,77 4,14 3,59 3,11 2,68 2,31 Among +6 and 0C is intented under the liquid. Among 0 and -20C is intended under the ice.
2,76 2,74 2,71 2,68 2,65 2,62 2,59 2,56 2,52 2,48 2,44 2,39 2,34 2,28 2,21 2,15 2,08 1,99
2,32 2,29 2,27 2,25 2,22 2,19 2,16 2,12 2,09 2,04 2,00 1,95 1,90 1,84 1,78 1,70
1,94 1,92 1,90 1,87 1,84 1,81 1,78 1,75 1,71 1,67 1,62 1,57 1,52 1,46
1,62 1,60 1,57 1,54 1,52 1,49 1,46 1,42 1,38 1,34 1,29 1,24
1,35 1,33 1,31 1,29 1,26 1,24 1,21 1,17 1,14 1,10 1,05
1,11 1,09 1,07 1,05 1,03 1,00 0,97 0,93 0,89
0,92 0,91 0,89 0,87 0,85 0,82 0,79 0,75
0,76 0,75 0,73 0,71 0,69 0,66 0,63
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7.8 Atmospheric moisture absorption by commercial calcium chloride

Commercial flake dihydrate calcium chloride (CaCl2.2H2O) has vapor pressure as shown below:
vapor pressure of commercial flake dihydrate CaCl2

60 50 temperature C 40 30 20 10 0 0 1 2 3 4 5 6 7 8 9 vapor pressure mmHg
Dihydrate flakes CaCl2 are hygroscopic and accordingly will absorb moisture readily from air of higher vapor pressure at the prevailing temperature. They are deliquescent since they will dissolve completely in its absorbed moisture, if the vapor pressure of the air equals or exceeds that of the saturated solution at the prevailing temperature. If the vapor pressure of the air is lower than shown for the saturated solution value in Table 5, anhydrous calcium chloride may be converted to the dihydrate, and the dihydrate may be converted to the tetrahydrate or to the hexahydrate; but no solution is produced in these cases. When calcium chloride deliquesces, or dissolves in moisture absorbed from the air, the solution produced is also hygroscopic and will continue to absorb moisture until an equilibrium condition is reached between the vapor pressure of the solution and that of the air. The solution will then try to maintain this equilibrium; it will give off moisture to the air if the humidity decreases and will absorb moisture when the humidity increases. The rate at which a given quantity of calcium chloride or calcium chloride solution absorbs atmospheric moisture is influenced by each of the following factors: Surface area exposed to the air, Rate of air circulation over the calcium chloride, and Difference between the vapor pressure of the air and that of the calcium chloride. The moisture absorption rate per unit weight of calcium chloride will increase whenever one or more of these factors are increased. The concentrations of the calcium chloride solutions in equilibrium with any given relative humidity of the air are shown in the following table:
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Atmospheric humidities in equilibrium with calcium chloride solutions at 25C

Relative Humidity Final solution %RH %w/w CaCl2 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 0,0 8,5 14,2 18,3 22,0 25,0 27,5 29,8 32,0 34,0 36,0 37,9 39,9 42,1 44,5 weight of water (approximate) absorbed per weight of CaCl2 Flakes Dihydrate 0,0 8,2 4,5 3,3 2,5 2,1 1,8 1,6 1,4 1,3 1,2 1,1 1,0 0,9 0,8 Anhydrous 10,2 5,7 4,2 3,3 2,8 2,5 2,2 2,0 1,8 1,6 1,5 1,4 1,3 1,1
The equilibrium conditions vary slightly for different temperatures, but for general purposes the values obtained at 25C are representative of average summer conditions. These are shown in the previous table, together with the indication of the weight unit of water absorbed per weight unit of calcium chloride consumed in producing the final solution. These values have been calculated considering 77.3% the CaCl2 content of dihydrate Flakes, and 94.9% that of CaCl2 anhydrous, using, at the end the following equation:
A
Where:
B C C
A = unit weight of water absorbed per unit weight of calcium chloride B = % actual CaCl2 in dihydrate flakes or anhydrous product C = % CaCl2 in final solution
Dehumidification with calcium chloride It is evident from the previous paragraph that either calcium chloride or its water solutions can be used to remove moisture from the air, if the vapor pressure of the air is higher than that of calcium chloride solution or hydrate used. Calcium chloride solution is generally used in a tower system in which the air is either passed through spray or bubbled through a solution of the calcium chloride. The solution can be maintained at its original concentration by passing a portion through a heat interchanger to evaporate and remove the absorbed moisture. Calcium chloride solid may be used in a tower system with the air passing up through the product, or in a basket type unit with the air passing over the surface of the exposed flakes. In either case provision must be made for a receiver to hold the calcium chloride solution produced and for disposal of this solution when the receiver is filled. In a tower system with air passing up through the calcium chloride, it is possible to produce exit air of about 7 to 10% RH by maintaining sufficient depth of fresh calcium chloride.
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In any arrangement the solution which drips from the calcium chloride is approximately a saturated solution containing 45-50% CaCl2. Since the concentration of the discarded solution determines the efficiency of the unit in terms of weight of water absorbed per weight of product consumed, it is desirable to provide some means for effective contact of the entering air with this solution prior to contact with the calcium chloride. In the ordinary basket type unit exposed flakes are soon coated with approximately a saturated solution and the exit air is in contact with this solution. The temperature and concentration of this calcium chloride solution then determines the minimum relative humidity to which the air can be reduced. In any air drying problem, the heat of condensation must be taken into account when water is removed from the atmosphere. This heat can be calculated from the latent heat of evaporation of water and the weight of condensed water. When drying air with calcium chloride, there is also the heat of hydration and heat of solution of the calcium chloride to be considered. Unless provision is made for removal of the heat produced during the absorption process some will be carried off in the exit air.
7.9 pH of calcium chloride solutions

The pH of water solutions freshly prepared from 78% flakes (Ca(OH)2 level of impurity = 2 g/kg) and pure (Ca(OH)2 absent) calcium chloride using demineralized water are tabulated below and shown graphically in Figure 5.
CaCl2 % w/w 1 5 10 15 20 25 30 35 40
pH of solution from pure CaCl2 7,90 7,45 6,90 6,45 5,90 5,40 4,85 4,30 3,85
pH of solution from 78% flakes CaCl2 9,85 10,05 10,10 10,00 9,80 9,70 9,20 8,75 8,10
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Figure 5 - pH of CaCl2 solutions
pH of solution from pure CaCl2 12,00 11,00 10,00 9,00 8,00 pH 7,00 6,00 5,00 4,00 3,00 2,00 0 5 10 15
pH of solution from 78% flakes CaCl2
20 CaCl2 %w/w
25
30
35
40
Figure 6 shows the neutralization curve of a technical CaCl2 35% solution prepared using CaCl2 78% flakes. Figure 6 - Neutralization curve CaCl2 35% solution
10 9 8 7 6 pH 5 4 3 2 1 0 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 liter HCl 33% per m3 CaCl2 35%
Freshly prepared calcium chloride solutions are somewhat alkaline due to the presence, in the commercial calcium chloride flakes, of a small percentage of free lime. The degree of ionization of this calcium hydroxide increases with increased water dilution as indicated by the higher pH of the weaker
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solutions. Although the solutions may show a relatively high pH they have little actual acid neutralizing value due to the small percentage of lime that is present. Calcium chloride solutions exposed to air will gradually absorb carbon dioxide to form calcium carbonate from the calcium hydroxide, thus reducing the alkalinity of freshly made solutions. Actually, this may in time progress beyond the neutral point, as pH values of 5 and 6 have been observed in unadjusted old calcium chloride solutions.
Evolution of pH CaCl2 solutions prepared using fresh water (hardness >30F) for dissolving flakes
pH Alkalinity as Ca(OH)2 g/kg
10,0 9,0 8,0 7,0 6,0

pH
0,10 0,09 0,08 0,07 0,06 0,05 0,04 0,03 0,02 0,01 0,00 0 5 10 15 20 25 % w/w CaCl2 30 35 40 45 50
Alkalinity as Ca(OH)2 g/kg
5,0 4,0 3,0 2,0 1,0 0,0
Ionization and the Meaning of pH The degree of alkalinity or acidity of any water solution of acids, bases and salts may be expressed in terms of pH values and determined by either electrometric or colorimetric methods. The former is the more accurate, but requires special apparatus and considerable experience for reliable results. Colorimetric procedures, employing a series of color standards, or paper indicators, designed especially for the determination of free hydrogen and hydroxyl ions, are useful for routine checking purposes. The symbol pH is used to designate hydrogen ion concentrations numerically, thus expressing the degree of acidity or alkalinity on a definition scale, analogous to the thermometric scale whereon temperature is expressed in degrees. On the pH scale, the value 7 represents the hydrogen ion concentration of a neutral solution; values numerically lower than 7 indicate increasing acidity, and higher values indicate progressive alkalinity. When acids, bases and salts are dissolved in water, more or less of their molecules are broken up (dissociated) into their constituent radicals or ions. The strength of an acid or a base increases with the extent of such dissociation or ionization. An alkaline solution is one in which the number of hydroxyl ions (OH-) exceeds the hydrogen ions (H+). In an acid solution the hydrogen ions predominate, but both ions are present, as water itself ionizes to a small extent, that is
H 2 O H OH
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The pH value is the logarithmic of the reciprocal, or the negative logarithmic of the number of hydrogen gram-ions per liter of solution. For example, pH 4 means that number of hydrogen gram-ions per liter of which -4.0 is the logarithm, that is, 0.0001 hydrogen gram-ions. The relationship between hydrogen ion and hydroxyl ion concentration, as tabulated on the next page, is based on the equation: Concentration of H ions x concentration of OH ions = a constant In concentrations that are dilute, or only moderately concentrated, @ 25C the constant is 10-14, and the equation becomes: H gram-ions per liter x OH gram-ions per liter = 10-14 Since temperature affects the extent of ionization of dissolved acids, salts and bases, as well as water, it follows that it influences the hydrogen ion concentration and the determination of pH. The effect of temperature upon the exponent in the constant 10-14 and the resulting pH of the neutral point will be evident from the values of the ionization-exponent of water at various temperatures, derived from International Critical Tables: Temperature C 5C 15C 25C 35C 45C 60C 100C Ionization EXP 14.72 14.34 13.99 13.67 13.39 13.03 12.29 Ph 7.36 7.17 7.00 6.89 6.69 6.51 6.15
For pure water and neutral solutions @ 25C, the expression is: 10-7 hydrogen concentration x 10-7 hydroxyl concentration = 10-14 pH 7 pOH 7
It will be evident that both acidity and alkalinity may be expressed in terms of pH and that it is unnecessary to refer to hydroxyl ion concentrations even in highly alkaline solutions. Alkalinity expressed by pH must not be confused with total alkalinity which is commonly determined by titration with a standard acid solution. pH is a measure of the hydroxyl ion concentration of an alkaline solution, whereas titration is a measure of its acid neutralizing capacity.
7.10 Surface tension

The surface tensions of solutions of pure calcium chloride in contact with air are given in Table 7 and Figure 7. Intermolecular attraction in a liquid gives rise to different effects at the surface than in the interior where molecules are attracted equally in all directions; those at the surface are attracted inwards, thus resulting in surface tension. Surface tension is a factor in the property of forming emulsions and of wetting and spreading over solids. The relatively greater surface tension of strong calcium solutions is related to the difficulty of wetting clean dry surfaces by such solutions. This can, however, be influenced greatly by a small addition of certain surface active (wetting) agents which reduce the surface tension.
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Table 7 - surface tensions of pure calcium chloride solutions
Surface tensions of pure calcium chloride solutions Surface tension in dyne per centimeter % w/w CaCl2 @ 10C @ 25C 0 74,22 71,97 1,1 72,32 2,7 72,75 5,26 75,74 73,49 9,99 77,42 75,17 18,17 81,12 78,87 24,98 85,22 82,97 30,75 89,17 86,92 35,69 90,37 43,75 97,07 55,42 106,97
Figure 7- surface tensions of pure calcium chloride solutions
110 105 100 dynes per cm 95 90 85 80 75 70 0 5 10 15 20 25 30 35 40 45 50 55 60 % w/w calcium chloride

@ 10C @ 25C
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7.11 Viscosity
The viscosities of calcium chloride solutions (Figure 8) vary greatly according to concentration and temperature: they increase with an increase in concentration at constant temperature, and decrease with an increase in temperature at constant concentration. Figure 8 - viscosities of calcium chloride solutions
18 17 16 15 14 13 12 11 viscosities -cP 10 9 8 7 6 5 4 3 2 1 0 5 10 15 20 25 30 35 40 % w/w calcium chloride

@ -25C @ -20C @ -15C @ -10C @ 0C @ +10C @ +18C @ +25C @ +40C
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7.12 Dilution of calcium chloride solutions

When diluting strong solutions to specified weaker ones, the first requirement is to know the exact CaCl2 content of the stronger solution. For this purpose, a densimeter may be used, and the corresponding percent CaCl2 found in Table 1. All values for concentrations as high as 40% CaCl2 are found in this table. Concentrations above 40.8% CaCl2 contain suspended crystals @ 15.6C, and therefore, densimeter readings at 15.6C are of little value. Concentrations between 40 and 45% can be determined fairly accurately, however, with the densimeter at a temperature above 15.6C by means of Table 3 and 4. For concentrations higher than 45% the CaCl2 content should be determined by chemical analysis or it may be arrived at indirectly by trial dilution as follows: Dilute a known weight of the strong solution with an equal weight of water, cool to 15.6C and determine the specific gravity. The concentration of the diluted solution, as determined from Table 1, multiplied by two, gives the CaCl2 content of the original strong calcium chloride solution. For example, if a known weight of strong calcium chloride solution is diluted with an exactly equal weight of water, cooled to 15.6C, and, by densimeter, is found to have a specific gravity of 1.351 kg/l, the corresponding concentration is, according to Table 1, 35% CaCl2. Multiplying by two gives the CaCl2 content of the original strong solution as 35.0 x 2 = 70.0% CaCl2. This method applies regardless of whether the original sample is in a completely liquid or solid condition. If it contains both solid and liquid, it is desirable to heat until the solid material is dissolved and a uniform sample can be obtained. Dilution calculations are made in accordance with the formula:
V
Where:
100 H A B (Equation 1) B
V = parts (volumes) of water required per 100 parts (volumes) of original strong solution. A = percent of calcium chloride in original strong solution. B = percent of calcium chloride desired in diluted solution. H = specific gravity of original strong solution.
For example, assume that it is desired to prepare a 23% CaCl2 solution from a stronger solution of 1410 kg/l specific gravity at 15.6C. From Table 1, it is found that a calcium chloride solution of 1410 kg/l corresponds to 40.0% CaCl2. Substituting in the equation 1:
100 1,410 40 23 104.2 23
parts of water to add each 100 parts by volume of original strong solution.
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If it is desired to use weight instead of volume units, and this is necessary when the original strong solution is above about 40%, the formula is simplified to:
W
Where:
100 A B (Equation 2) B
W = parts (weight) of water required per 100 parts (weight) of original strong solution.
If it is desired to use a weak calcium chloride solution, instead of water, for dilution of a stronger solution, equation 1 is modified to:
V
Where:
100 H A B (Equation 3) R B C
V = parts (volumes) of weak solution required per 100 parts (volumes) of original strong solution. A = percent of calcium chloride in original strong solution. B = percent of calcium chloride desired in diluted solution. C = percent of calcium chloride in the diluting solution. H = specific gravity of original strong solution. R = specific gravity of the diluting solution.
To obtain results by weight instead of by volume, the specific gravity expressions are deleted and the formula becomes:
100 A B (Equation 4) B C
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7.13 Specific heats

The specific heat of a liquid is in the ratio of the quantity of heat required to raise the temperature of a unit weight of the substance one degree to that required to raise the temperature of an equal weight of water one degree at any specified temperature. Table 8 shows the specific heats of pure calcium chloride solutions. Table 8 - specific heats of pure calcium chloride solutions
Specific heat in calories per gram % w/w @ -40C @ -30C @ -20C @ -10C CaCl2 8 9 10 11 12 13 14 15 16 0,768 17 0,756 18 0,745 19 0,734 20 0,723 21 0,713 22 0,695 0,704 23 0,686 0,694 24 0,678 0,686 25 0,670 0,678 26 0,656 0,663 0,670 27 0,649 0,656 0,663 28 0,636 0,642 0,649 0,656 29 0,634 0,639 0,644 0,649 30 0,631 0,635 0,638 0,643 @ 0C 0,882 0,867 0,853 0,839 0,825 0,812 0,799 0,787 0,775 0,763 0,752 0,741 0,731 0,721 0,711 0,702 0,693 0,685 0,677 0,669 0,662 0,655 0,649 @ +10C @ +20C @ +30C @ +40C @ +60C @ +80C @ +100C 0,887 0,872 0,858 0,844 0,831 0,818 0,805 0,793 0,781 0,770 0,759 0,748 0,738 0,728 0,718 0,709 0,700 0,692 0,683 0,676 0,669 0,662 0,655 0,892 0,877 0,863 0,849 0,836 0,823 0,811 0,799 0,787 0,775 0,764 0,754 0,744 0,733 0,724 0,715 0,706 0,698 0,690 0,682 0,675 0,668 0,661 0,897 0,882 0,868 0,855 0,842 0,829 0,817 0,805 0,792 0,780 0,769 0,759 0,749 0,739 0,729 0,721 0,712 0,704 0,696 0,689 0,682 0,675 0,668 0,900 0,870 0,844 0,821 0,796 0,773 0,755 0,735 0,720 0,703 0,688 0,675 0,910 0,881 0,857 0,834 0,808 0,787 0,768 0,749 0,731 0,717 0,701 0,688 0,920 0,891 0,869 0,845 0,820 0,799 0,780 0,761 0,745 0,730 0,715 0,700 0,930 0,901 0,879 0,858 0,832 0,810 0,791 0,772 0,758 0,741 0,729 0,712
7.14 Heat of solution of calcium chloride

Considerable caution must be exercised when dissolving large quantity of calcium chloride in water due to the high heat of solution. Depending upon the water temperature and the ambient temperature a temperature increase to above 90C may be experienced. Table 9 contains results of observations when dissolving 78% flake calcium chloride in water using an insulated flask. Table 9 - T increase in dissolving flake in water @ 15.6C
Final solution Density @ 15.6/15.6C % w/w CaCl2 1,073 8,4 1,135 15,1 1,190 20,6 1,242 25,3 1,286 29,2 1,324 32,7 1,334 35,6
Temperature rise C 10 18 26 33 38 41 43
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The heat evolved when dissolving pure anhydrous calcium chloride in water is shown in Table 10. The temperature increases shown in the last column of the table are calculated under the assumption that no heat is lost to the surroundings and, therefore, may be considered to be a possible, but not probable, maximum. Table 10 - Heat evolved in dissolving anhydrous CaCl2 in water
grams of water per mole CaCl2 7200 3600 1800 900 360 180 108
Heat evolved % w/w CaCl2 1,5 3,0 5,8 11,0 23,6 38,1 50,7 Gram calories per mole CaCl2 17921 17921 17754 17635 17037 15412 13381
Approximate temperature rise C 0,25 0,50 1,00 20,50 51,00 89,00 111,00
The quantity of heat evolved in dissolving the hydrates of calcium chloride is somewhat less than that for the anhydrous product, which decreases as the number of molecules of water increases. It is a positive heat of solution in each case except when dissolving the hexahydrate, CaCl2.6H2O, which has a negative heat of solution and actually lowers the temperature of the water during dissolving.
7.15 Heat of dilution and heat content of calcium chloride solutions

The heat evolved when a strong calcium chloride solution is diluted with water or with a weaker calcium chloride solution, and other problems involving heat and temperature changes, may be calculated from the data on specific heats and total heat contents (enthalpy) of calcium chloride solutions. The enthalpy-concentration data for pure calcium chloride solutions are shown in Table 11. The reference state for these data, as in steam tables, is liquid water at 0C and 1 atmosphere, at which the heat content of liquid water is considered to be zero, and that of the calcium chloride solution is equal to its heat of solution. The values shown are used in the same manner as are those from a steam table. The red bold values in Table 11 represent the heat contents of the liquid only, while those in black are the heat contents of mixtures of ice and liquid or the hexahydrate form and liquid in the case of the 32% CaCl2 solution. The composition of the solution containing 29.8% is that of the eutectic mixture which remains liquid down to -55C. The data were calculated using specific heats, heats of solution and ice-saturation data for pure calcium chloride solutions as reported in this bulletin. The heat of fusion and specific heats of ice were obtained from Bulletin of the Bureau of Standards.
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Table 11
T C 30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30 -35 -40 -45 -50 -55
Table 11 - Enthalpy of pure calcium chloride solutions-cal/g % w/w CaCl2 0,0 5,0 10,0 12,5 15,0 17,5 20,0 22,5 25,0 27,5 29,8 30,1 36,0 41,9 44,8 47,6 50,5 53,4 56,4 59,3 61,8 64,1 25,1 31,3 37,5 40,6 43,6 46,5 49,6 52,8 55,7 58,4 60,7 20,1 26,6 33,2 36,4 39,6 42,8 45,9 49,2 52,2 55,0 57,4 15,1 22,0 28,9 32,2 35,6 38,9 42,2 45,5 48,7 51,5 54,0 10,1 17,4 24,6 28,1 31,6 35,0 38,5 41,9 45,1 48,1 50,8 5,1 12,8 20,3 24,0 27,7 31,2 34,8 38,3 41,7 44,8 47,5 0,0 8,2 16,0 19,8 23,7 27,4 31,1 34,8 38,2 41,4 44,3 -81,2 -32,8 11,7 15,7 19,8 23,6 27,5 31,2 34,8 38,1 41,0 -82,6 -50,8 -16,8 0,1 15,9 19,8 23,9 27,6 31,3 34,8 37,8 -83,9 -58,6 -30,0 -15,7 -1,4 12,8 20,2 24,1 27,9 31,4 34,6 -85,2 -63,9 -38,3 -25,4 -12,6 0,2 13,1 20,6 24,5 28,1 31,4 -86,5 -68,2 -44,5 -32,7 -20,9 -9,0 2,8 15,1 21,1 24,8 28,1 -87,7 -71,9 -49,7 -38,6 -27,5 -16,3 -5,2 5,9 17,0 21,5 25,0 -89,0 -75,1 -53,9 -43,3 -32,1 -22,0 -11,5 -0,7 10,5 18,2 21,8 -90,2 -78,0 -57,4 -48,4 -36,9 -26,6 -16,3 -6,1 4,2 14,2 18,6 -91,4 -80,7 -60,7 -50,7 -40,6 -30,7 -20,6 -10,6 -0,7 9,4 15,5 -92,6 -83,2 -63,7 -53,9 -44,1 -34,4 -24,6 -14,8 -5,1 4,7 12,3 -93,7 -85,7 -66,6 -57,0 -47,4 -37,9 -28,3 -18,7 -12,0 0,4 9,2
32,0 66,1 62,8 59,5 56,4 53,2 50,0 46,8 43,7 40,5 37,4 34,3 31,2 28,1 25,0 19,0 13,9 8,8 3,6
Below -55C, solid mixture of ice and hexahydrate calcium chloride To obtain BTU/pound, to multiply cal/g by 1.7986
The following will illustrate some of the uses for Table 11. Illustration 1 32% calcium chloride at 30C is diluted with water at 5C to give a solution containing 20% CaCl2. (a) how much heat must be removed in order to maintain a final temperature of 5C? (b) what will be the final temperature if no heat escapes during the mixing? Answer to question (a) Taking 100 g of the original 32% solution as a basis for the calculation, the weight of water to be added to give the desired 20% CaCl2 is obtained by use of the dilution equation 2,
100 A B 100 32 20 60 B 20
g of water required
From Table 11: 1. 2. 3. Heat content of 32% CaCl2 solution at 30C Heat content of 20% CaCl2 solution at 5C Heat content of water at 5C = 66.1 cal per g = 34.8 cal per g = 5.1 cal per g
Let Q = heat to be removed per 100 g of 32% CaCl2 solution in order to maintain a final temperature of 5C. The heat balance is (100 x 66.1)+(60x5.1)=(160x34.8)+Q, from which Q=1348 cal/g
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Answer to question (b) If no heat is removed Q=0. The heat content (H) of the final solution will be: (100x66.1)+(60x5.1) = 160H, from which H=43.2 cal/g. Reference to Table 11 shows that 1 g of 20% CaCl2 solution must be at approximately 17C to have a heat content of 43.2 cal; therefore, the temperature of the final mixtures is 17C if no heat escapes.
7.16 Thermal conductibility

Table 12 - thermal conductivity of calcium chloride solutions
Thermal conductivity - kcal/m C h Specific % w/w gravity CaCl2 1 0,1 1,01 1,3 1,02 2,5 1,03 3,6 1,04 4,8 1,05 5,9 1,06 7,1 1,07 8,3 1,08 9,4 1,09 10,5 1,1 11,5 1,11 12,6 1,12 13,7 1,13 14,7 1,14 15,8 1,15 16,8 1,16 17,8 1,17 18,9 1,18 19,9 1,19 20,9 1,2 21,9 1,21 22,8 1,22 23,8 1,23 24,7 1,24 25,7 1,25 26,6 1,26 27,5 1,27 28,4 1,28 29,4 1,286 29,9 1,29 30,3 1,3 31,2 1,31 32,1 1,32 33 1,33 33,9 1,34 34,7 1,35 35,6 1,36 36,4 1,37 37,3 @ 0C 0,487 0,486 0,484 0,483 0,482 0,481 0,480 0,479 0,478 0,477 0,475 0,474 0,473 0,472 0,471 0,470 0,469 0,468 0,467 0,466 0,465 0,464 0,463 0,462 0,460 0,459 0,457 0,455 0,454 0,454 0,453 0,452 0,452 0,451 0,451 0,450 0,449 0,448 0,447 @ -10C @ -20C @ -30C @ -40C @ -50C
0,459 0,458 0,457 0,456 0,455 0,454 0,453 0,452 0,451 0,450 0,449 0,448 0,447 0,446 0,445 0,444 0,443 0,443 0,442 0,440 0,439 0,438 0,437 0,436
0,441 0,440 0,439 0,438 0,437 0,436 0,435 0,434 0,433 0,432 0,432 0,431 0,428 0,428 0,426
0,425 0,424 0,423 0,422 0,421 0,420 0,419 0,418 0,417
0,411 0,410 0,409 0,409 0,408
0,399 0,398 0,398
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7.17 Specific problems of technical calcium chloride solutions

Cloudy liquid Brown liquid There are two reasons for a cloudy liquid: the liquid is delivered in this state straight from the factory, the liquid is made by dissolution of solid products
Origin of the problem Turbidity of solutions may be caused by: Calcium sulphate [CaSO4]: this insoluble salt, which is generally present in the calcium chloride produced by the Solvay process, is non-toxic and stable. Its presence may be detected by acidifying the liquid with hydrochloric acid (pH <1). When the solution is acidified, at room temperature, the insoluble salt remains visible, while at 80-90C the insoluble salt disappears. Calcium hydroxide [Ca(OH)2]: generally used by factories to maintain the pH level of solutions during evaporation (7 < pH < 9.5), lime gives better protection of installations against corrosion. It may be found in the end products where it causes cloudiness. When the pH is high, the cloudiness is impossible to be removed by filtration. Only a slight acidification (with HCl) can resolve the problem (pH 3.5 approx). Calcium carbonate [CaCO3]: this substance often results from a reaction between bicarbonates (HCO3-) present in the water used for dissolution/dilution (hard water) and natural lime in calcium chloride. It can be a nuisance for certain applications but may be eliminated by slight acidification. Iron hydroxide [Fe(OH)3]: this substance often results from a reaction between the (OH) in the lime and the iron in the solution. In an acid environment the precipitate disappears and the color of the solution then ranges between yellow and brown depending on the iron content. Sodium chloride [NaCl]: salt is a raw material of the Solvay manufacturing process and can be found as a contaminant of the calcium chloride. It causes no problems in applications where it is not crystallized (high dilution, high temperature of solutions). It is generally inevitable. It is easily identifiable by slightly diluting the NaCl-saturated solution in water, which dissolves the precipitated NaCl.
Origin of coloration Coloration is generally caused by the presence of iron in solution or solid products. Different colors may occur depending on the concentration of iron and its state of oxidation (black, grey, brown, red, orange or yellow). Problems associated with the presence of (OH)- and CO3= Hydroxides (OH)- and carbonates (CO3)= may favor the presence of calcium carbonate which may crystallize installations in the form of scaling (blocking pipe work poor quality of finished products). Chemical identification of these substances in the calcium chloride may help . The chemical reactions that we use are the following: Ca(OH)2 + HCl CaCl2 + H2O CaCO3 + 2HCl CaCl2 + H2O + CO2 CaCl2 + 2KOH Ca(OH)2 + 2KCl Ca(OH)2 + CO2 CaCO3 + H2O 2+ CaCl2 + CO(OH) + H2O CaCl2 + Ca + OH + CO2
With time: With water:
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Rise in pH 1 pH unit = 58 mV (potentiometric analysis). The method used is titred alkalimetry (TA) and complete titre alkalimetry (CTA). Note that in practice the amount of carbonate in our products is very low and that the majority of problems encountered are due to the use of hard water. In this case, there will inevitably be a parasitic reaction:
Ca(OH)2 + Ca(HCO3)2 2CaCO3 + 2H2O Case 1: presence of OH
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Case 2: presence of OH and CO3
Case 3: presence of CO3 and HCO3
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Case 4: presence of CO3=
Corrosion of metals Calcium chloride solutions are not inherently corrosive to iron and steel in the sense that acids are corrosive. Repeated experiments by several investigators have demonstrated that such solutions usually are no more corrosive than plain water. Steel specimens submerged in calcium chloride solutions not exposed to air remain practically unattacked for long periods. However, if the solution is exposed to air or strongly aerated, there is rusting just as is the case if plain water is aerated. Iron or steel specimens wet with calcium chloride solutions and left exposed to the air undergo rusting, but to no greater extent than similar specimens kept wet with a film of plain water. However, there is this difference, under normal atmospheric conditions, the water evaporates and the rusting stops, whereas the calcium chloride solution does not dry readily, and the rusting therefore continues over a long period. As a matter of practical experience, ordinary steel tanks and pipe lines give very satisfactory service. A common example is the refrigeration plant where calcium chloride brine is used extensively. There are also large numbers of steel tank cars and storage thanks which have been in service for many years. Calcium chloride solutions are slightly alkaline due to a fractional percentage of calcium hydroxide (lime) that is present. Such solutions attack aluminum, zinc or tin, and alloys of these metals, due to the alkaline condition of the freshly prepared solutions. It is well to avoid these metals in calcium chloride brine systems, although galvanized (zinc coated) ice cans are commonly used in such systems without appreciable damage when the pH of the solution is maintained near the neutral point. Any solution of calcium chloride is an electrolyte (conductor of electricity), as are all water solutions of other inorganic salts. A possibility of galvanic type corrosion can occur in electrolytes whenever two or more dissimilar metals are in electrical contact. It is desirable, therefore, to avoid the use of adjacent dissimilar metals in contact with calcium chloride solutions. A second type of electrolytic corrosion may be caused by leakage of an electric current from a system not properly insulated or grounded. Testing around the corroded parts with a voltmeter or ammeter will locate the source of this trouble, which may then be corrected.
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The addition of certain materials known as inhibitors has been found to help materially in preventing or minimizing the corrosion of steel and other common metals by salt solutions. The use of chrome compounds, such as sodium chromate or sodium bichromate is quite common in the refrigeration brines. The usual recommendation is 2 kgs per cubic meter of calcium chloride brine. Preventing corrosion In answer to questions from customers concerning the protection of installations against corrosion, you may reply as follows: Corrosion of installations may be prevented by following the instructions below: eliminate electrochemical couples: give preference to ferrous metals which are neither coated nor galvanized, and avoid the simultaneous presence of two different types of metal. For example, avoid the simultaneous use of zinc galvanized ion with copper (in particular, avoid installing a copper coil in a galvanized vat). Separate elements made of different types of metal using electrically insulating joints (rubber, ). Maximize the use of pipe work made of ABS or compatible plastic materials. Prescribe the use of tin-based solder, especially in presence of copper. If pipe work has to be welded, arc or oxy-acetylene welding should be used. Prevent air from entering the brine, in other words: . prevent the brine from coming into contact with air and fit covers to all vats and tanks, . avoid letting the solutions fall through the air and avoid turbulence; brine should always be introduced into vats, tanks and other apparatus from below, . use primed pumps to prevent air entering via seals, . any stirring should be carried out slowly and as deep as possible inside the vats, . keep the installations under a nitrogen atmosphere. Avoid direct contact between the installation and metallic elements of the surrounding building: e.g. metal pillars, concrete reinforcing; it should therefore be electrically insulated from these elements and from the ground. Certain coatings: (tar-based or bituminous paints, epoxy paints, ) protect metallic installations against corrosion. You must however ensure that they are completely hermetic; otherwise they may lead to dangerous local corrosion due to differential aeration. Maintain the pH of the brine: it is recommended to keep the pH of the solution either alkaline (from 9 to 10), or neutral (from 7.5 to 8), depending on the construction of the circuit and according to the instruction below.
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Since the pH has a natural tendency to fall whatever precautions are taken, it must be regularly monitored using the following methods: pHmeter, indicator papers, pH indicators which change color (phenolphthalein or methyl orange).
pH correction may be achieved using one of the following reagents: raising pH: quicklime or slacked lime (beware of slacking) or caustic soda. lowering pH: hydrochloric acid.
Use corrosion inhibitors: a growing number of corrosion inhibitors are available on the market. They may generally be used without any serious risk. Nevertheless, their suitability for use in food processing should be verified for this type of application.
ANALYTICAL METHODS
The analytical methods described as follows are just an indication, and are based on the principles we are using to verify the purity of CASO calcium chloride. All the official documents are managed by the Quality Responsible Manager of the Production Unit within the ISO Quality System. For more details on tests we made, please take a look at our commercial document ANA-CC 40 00 00.
8.1 Total Calcium (Ca) EDTA potentiometry test

Reagents EDTA solution 1 N Demineralised water (electric conductivity lower than 1 microS/cm) Nitric acid, approximately 2 N pH 10 buffer solution
Weigh accurately 25/50 grams of flakes/granules calcium chloride and transfer to a 500-ml volumetric flask, adding 200 ml of demineralized water to dissolve the product. Add 25 ml of Nitric acid,, mix well and dilute to the mark using demineralized water. Transfer by pipette, 10-ml of prepared solution of flakes 5-ml of prepared solution of granules into a 250-ml beaker and add 100-ml of demineralised water. Add 10-ml of pH 10 buffer solution. Titrate the solutions using 1 N EDTA solution (A-ml) to the equivalent point measured by amalgamate silver electrode.
8.2 Alkalinity as Ca(OH)2 Phenolphthalein test

Reagents Hydrochloric acid 0.1 N Phenolphthalein indicator 4 g/l Demineralised water (electric conductivity lower than 1 microS/cm) Weigh 25 grams of flakes/granules calcium chloride in a 500-ml beaker and dissolve in approximately 150-ml of demineralized water. Titrate the solution with 0.1 N hydrochloric acid solution (A-ml) using 3-4 drops of phenolphthalein indicator 4 g/l to the colorless end point.
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8.3 Sulfates (CaSO4) Ionic chromatography method

Reagents Demineralised water (electric conductivity lower than 1 microS/cm) Demineralized water MillQ Mother solution for anions elution at 8.0 mM Na2CO3/1.0 mM NaHCO3 (in a 250-ml flask, weigh 2.095 g of NaHCO3 + 21.778 g of Na2CO3; dissolve using MilliQ water and dilute to the mark) Nitric acid 2 N Weigh 25/50 grams of flakes/granules calcium chloride in a 500-ml volumetric flask and dissolve in 200ml of demineralized water. Add 25-ml of Nitric acid and diluted them to the marks using demineralized water. Transfer by pipette 5-ml of prepared solution of flakes 2-ml of prepared solution of granules
into a 200-ml volumetric flask and diluted them to the mark using demineralized water. Use the ionic chromatograph for measuring SO4 content (A mg/l).
8.4 Iron (Fe) Spectrophotometric test

Reagents Demineralised water (electric conductivity lower than 1 microS/cm) Phenolphthalein indicator 4 g/l Hydrochloric acid 33% or 37% Hydrochloric acid 1 N Caustic soda 1 N - dipyridyle solution 1 g/l Weigh accurately, 0.5 grams of - dipyridyle, transfer them to a 500-ml volumetric flask, and dissolve in demineralised water; add 10-ml of Hydrochloric acid 1 N, diluted to the mark and mix well. hydroxylamine chlorohydrate solution 100 g/l Weigh accurately, 50 grams of hydroxylamine chlorhydrate (HONH3Cl), transfer them to a 500ml volumetric flask and diluted to the mark with demineralised water. Ammonium acetate buffer solution 200 g/l approx Weigh 40/20 grams of flakes/granules calcium chloride in a 600-ml beaker and dissolve in 150-ml of demineralized water. Add 6-ml of concentrated hydrochloric acid. Boil the solution for 10 minutes and then let it cool. Transfer the solutions in two 250-ml volumetric flasks and diluted them to the marks using demineralised water. For each sample (blank solution inclusive): Introduce 10-ml of solution in a 50-ml emery plug graduated-cylinder and adding 30-ml of demineralised water. Than, in sequence (mixing the solution after each addition) add: . 1-ml of hydroxylamine chlorohydrate solution and wait for a minute, . 5-ml of Ammonium acetate buffer solution and, . 1-ml of - dipyridyle solution. Dilute to the mark with water demineralization, and mix well. Using a wavelength setting of 520 nm, adjust the spectrophotometer to zero absorbance against blank solution in a 40-mm absorption cell. Then obtain the absorbance of the sample(s) in the same cell(s) - (A, g of Iron).
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8.5 Water insoluble matter Gravimetric method

Reagents Demineralised water (electric conductivity lower than 1 microS/cm) Silver nitrate 0.1 N solution Phenolphthalein indicator 4 g/l Weigh 200 grams of flakes/granules calcium chloride in a 1.000-ml beaker and dissolve in 400-ml of demineralised water previously heated up to 50 C. Let the solution in stand-by for 5 minutes. Prepare a 5 Millipore filter and conditioner it at 100 C for 30 minutes and, after, place it into a dryer for 15 minutes. Weigh the filter (P1-g). Filter the solution through the prepared filter, washing the precipitate free of chlorides with hot water (7080 C. Normally, 8-10 washing operations, using 15 ml of water approx, needs. This step is not used for granules). Dryer the filter for 1 hour and, after, place it into a dryer for 15 minutes. Weigh the filter (P2-g). Water insoluble matter g/kg = (P2 P1) * 5
8.6 Turbidity spectrophotometer test

Reagents Demineralised water (electric conductivity lower than 1 microS/cm). Weigh 10/30 grams of flakes/granules calcium chloride in a 250-ml beaker and dissolve in 90/50-g of demineralized water up to complete dissolution. Using a wavelength setting of 585 nm, measure the absorbance of the solution in a 40-mm absorption cell (E, absorbance). Turbidity will be expressed as E*1000/cm
8.7 Granulometry automatic sieve test

Sieve tests, to be comparative, should be made under the same conditions using the same amount of material. Tests made with a mechanical sifter are the most reliable. This test should be made in a dry atmosphere and as rapidly as possible with minimum exposure to the air. Following the test, the sieves should be washed thoroughly and dried. Materials Technical balance. Series of DIN sieves (diameter 200 mm) 8, 5, 4, 2.8, 2, 1.25, 1, and 0.5 mm, with cap and bottom pan. Automatic sifter.
Weigh the sieves (bottom pan inclusive) and stack them in order of size, with the largest opening on top and the smallest on the bottom. Weigh 50/100-g of calcium chloride (P) and place it in the top sieve after making certain the bottom pan is in place. Cover, place in the sifter, and operate the machine for 3 minutes (2 minutes for CaCl2 Powder). Brush each separated portion onto a piece of paper and weigh on a balance to the first decimal place. Results should be reported as % through a certain sieve, on a certain sieve, for each portion. Results: % through sieves (example for Flakes) A1 to A6, grams, weight of 8, 4, 2, 1, 0.5 sieves and bottom pan, totally empty.
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B1 to B6, grams, weight of 8, 4, 2, 1, 0.5 sieves and bottom pan, with product sieved. For each sieve, we should calculate the weight (Px, grams) of product refused by each one. P1 = B1 A1 (8 mm sieve) P2 = B2 A2 (4 mm sieve) P3 = B3 A3 (2 mm sieve) P4 = B4 A4 (1 mm sieve) P5 = B5 A5 (0.5 mm sieve) P6 = B6 A6 (bottom pan) < 0.5 mm [%] = P6 * 100/P < 1.0 mm [%] = (P6 + P5) * 100/P < 2.0 mm [%] = (P6 + P5 + P4) * 100/P < 4.0 mm [%] = (P6 + P5 + P4+ P3) * 100/P < 8.0 mm [%] = (P6 + P5 + P4+ P3 + P2) * 100/P Sieved (mm) 0.500 1.000 1.250 2.000 2.800 4.000 5.000 8.000 Flakes Yes Yes Yes Yes Yes Powder Yes Yes Granules Yes Yes Yes Yes Yes Yes
The above information are provided for our customers only (and we accept no liability to any third parties) and reflects our current knowledge and experience of the product. All products are supplied in accordance with the relevant conditions of sale of the SOLVAY invoicing company. Solvay can accept no liability for the effects of any chemical combinations or mixtures of the product which are carried out by our customers or third parties. In using the product our customers are reminded to comply with all relevant legal, administrative and regulatory requirements and procedures relating to its use and the protection of the environment. Rev.2, February 2013
page 59 of 59

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Products, Applications, Safety, Handling and Storage, Characteristics, Methods

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY, THE COMPANY

1.2 Solvay Mission and Vision

1.3 Solvay Values

SOLVAY CASO calcium chloride HANDBOOK

1.4 Solvay Code of Conduct

1.9 Public authorities

1.10 General public

SOLVAY CASO calcium chloride HANDBOOK

CASO CALCIUM CHLORIDE

2.1 Production Process

SOLVAY CASO calcium chloride HANDBOOK

2.2 The benefits

2.3 Commercial grades

SOLVAY CASO calcium chloride HANDBOOK

2.4 Production Plant

Company name: Address: Zip Code: City: Country: Phone: Fax:

SOLVAY CASO calcium chloride HANDBOOK

MAIN USES OF CASO CALCIUM CHLORIDE

3.1 Food & Agro-Food industry

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY CASO calcium chloride HANDBOOK

3.2 Animal nutrition

SOLVAY CASO calcium chloride HANDBOOK

3.3 Serving the chemical industry

3.4 Oil & Gas Industry

SOLVAY CASO calcium chloride HANDBOOK

3.5 From earth to concrete

SOLVAY CASO calcium chloride HANDBOOK

3.6 Helping the environment

SOLVAY CASO calcium chloride HANDBOOK

3.8 Domestic dehumidification

3.9 Winter road treatment

SOLVAY CASO calcium chloride HANDBOOK

7 2 NaCl 3 MgCl2 3 Urea KCl CMA

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY CASO calcium chloride HANDBOOK

3.10 Anti-Dust treatment

External Temperature, C 10 20 30 40 50 60 Starting of crystallization of solution, C -6 -12 -20 -33 -50

SOLVAY CASO calcium chloride HANDBOOK

CASO LIQUID 36%

SOLVAY CASO calcium chloride HANDBOOK

SAFETY & ENVIRONMENT

Products concerned: dihydrate and liquid CaCl2

Products concerned: anhydrous CaCl2

SOLVAY CASO calcium chloride HANDBOOK

Handling and Storage

6.1 Dry calcium chloride storage bins

SOLVAY CASO calcium chloride HANDBOOK

6.2 Dry calcium chloride conveyors and elevators

6.3 Storage tanks for liquid calcium chloride

6.4 Dissolving CASO

SOLVAY CASO calcium chloride HANDBOOK

SOLVAY CASO calcium chloride HANDBOOK

Chemical-physical properties of CASO calcium chloride

7.1 Properties of Anhydrous calcium chloride

7.2 Properties of the hydrates of calcium chloride

SOLVAY CASO calcium chloride HANDBOOK

7.3 Properties of calcium chloride solutions

SOLVAY CASO calcium chloride HANDBOOK