1. Lecture Topic 1: Introduction to the Chemical Industry Premise :In order to discuss the place of chemistry in industry, we must consider the nature of the “Chemical Industry” and related industries in terms of economics and fundamental philosophies. Goal :Students should be able to 1) describe the place of the “Chemical Industry” in the Canadian and world economy 2) describe the nature of the Canadian “Chemical Industry”

2. Chemistry and Industry The “Chemical Industry” a term referring to a statistical entity tracked by economic analysts includes the production of chemicals (pharmaceuticals, pesticides, etc.) and chemical products (plastics, paints, dyes etc.) traditionally, does not include production of steel, glass, paper etc. Other relevant industries steel aluminum glass ceramics pulp and paper petroleum natural gas etc.

3. Characteristics of the Chemical Industry 1) Basic objective - make a profit 2) Very competitive - there are hundreds of chemical companies, both small and very large…there tend not to be monopolies 3) Highly dependent on science and technology 4) Spends large amounts of its money on R&D 5) Large capital requirements - to construct, expand and maintain production facilities 6) Low labor requirements - BUT needs highly qualified personnel 7) Industry Growth - generally through integration rather than diversification

4. The Chemical Sector at a Glance Chemicals and chemical products: account for ~10% of total world trade in all commodities are the 2nd largest single item of global trade (road vehicles being the 1st). World Chemicals Output (2002): $1.6 Trillion USD ! Europe31% USA28% Asia/Pacific27% Other*14% *Other: Latin America, non-E.U. Europe, Africa, Oceania, Canada

5. The Chemical Sector at a Glance World’s largest chemical producer : U.S.A. (World’s largest chemical exporter : Germany) North American Chemicals Output (2002): $505 Billion USD USA92% ($467 Billion USD) Canada 5% ($23 Billion USD) Mexico 3% ($15 Billion USD)

6. Canada’s Chemical Leaders 1. Nova Chemicals (public) 2. Potash Corp. Sask. (public) 3. Dow Chemical Canada (100% Dow) 4. Agrium (public) 5. DuPont (77% DuPont) 6. Methanex (37% Nova) 7. Imperial Oil (70% Exxon-Mobil) 8. ICI Canada (100% ICI) 9. BASF (100% BASF) 10. Shell Canada (78% Royal Dutch Shell) 11. Celanese Canada (100% Celanese AG) 12. Petromont (50% Dow Chemical, 50% Prov. Quebec) 13. Rhône-Poulenc Canada (100% Rhône-Poulenc) 14. CXY Chemicals (100% Nexen) 15. AT Plastics (public)

7. Premise :There are fundamental differences between the design of a chemical synthesis for industry and that for a research laboratory. Goal :Students should be able to 1) explain how industrial synthetic approaches differ from laboratory synthesis methods. 2) evaluate possible reaction schemes based on thermodynamic, economic, and other considerations. Laboratory Chemistry vs. Industrial Chemistry

8. Differences in the Synthetic Approach e.g., formation of ethyl alcohol by hydration of ethylene: Laboratory Scale bubble ethylene into 98% H 2 SO 4 dilute and warm the reaction mixture to hydrolyze the resultant sulfate ester Industrial Scale a stream of ethylene is mixed with steam at 325°C and 1000 psi and passed over a solid catalyst consisting of phosphoric acid absorbed on diatomaceous earth; the process is run continuously, and unreacted ethylene is recovered and recycled to the feed stream.

9. Different Approaches for Different Objectives Laboratory Objectives synthesize the product in the most convenient manner considering: 1) chemist’s time 2) equipment available (usually must use glassware) 3) conditions achievable (usually close to ambient pressure and between -195.8° C (N 2(l) ) and 132° C (chlorobenzene). Industrial Objectives produce the product at minimum total cost on a scale that will generate the maximum economic return. may use: 1) large range of temperatures and pressures 2) batch process or continuous operation 3) reactants in vapor phase or liquid phase

10. Evaluation of a Reaction If a chemist has an idea for an industrial scale process, what are the steps that must be taken before the process can be implemented? 1) Evaluation of the reaction: Before any serious literature search or laboratory work is started, various possible strategies are proposed. 2) Economic feasibility 3) Technical feasibility 4) Other considerations: environmental issues, etc.

11. Evaluation of a Reaction The chemist must consider not only the well-known, obvious approaches, but also unknown or untested approaches. e.g., the manufacture of ethylamine

12. Economic Feasibility Estimate the difference between the market value of the products and the reactants. First approximation, assume: 1) 100% yield 2) no costs of solvents or catalysts 3) no value for co-products These assumptions must be reassessed further on in the development stage.

13. Technical Feasibility There are two basic questions that a chemist or chemical engineer must ask concerning a given chemical reaction: (1) How far does it go, if it is allowed to proceed to equilibrium? (Does it go in the direction of interest at all?) (2) How fast does it progress? Question (1) is concerned with thermodynamics and amounts to evaluating the equilibrium constant (K). Question (2) is a matter of kinetics and reduces to the need to know the rate equation and rate constants (k).

14. Technical Feasibility Generally, the first approach is to consider the thermodynamics of the reaction. This may be done by evaluating the change in Gibbs free energy (ΔG). ΔG R = ΔH R - T ΔS R A spontaneous reaction has a decrease in Gibbs energy of the system. To calculate the Gibbs energy of reaction, use standard Gibbs energies of formation ΔG f °. ΔG reaction = ΣΔG f ° products - ΣΔG f ° reactants

15. Example: Dissociation of ethyl chloride At 298 K ΔH f °-26.7012.50-22.06 ΔG f °-14.3416.28-22.77 S° At 1000 K ΔH f °-30.43 9.21-22.56 ΔG f ° 18.6028.85-24.08 S° 93.8072.07 53.25 ΔH rxn = ΔH f ° CH2=CH2 + ΔH f ° HCl - ΔH f ° CH3CH2Cl ΔG rxn = ΔG f ° CH2=CH2 + ΔG f ° HCl - ΔG f ° CH3CH2Cl ΔS rxn = S° CH2=CH2 + S° HCl - S° CH3CH2Cl

16. At 298 K: ΔH rxn = +17.14 kcal/mole ΔG rxn = +7.86 kcal/mole ΔS rxn = +31.15 cal/mole At 1000 K: ΔH rxn = +17.08 kcal/mole ΔG rxn = -14.43 kcal/mole ΔS rxn = +31.52 cal/mole - ΔG at 1000 K only! Change in Free EnergyIndication -ΔGpromising small +ΔGworth further investigation large +ΔGpossible only under unusual conditions

17. ΔG f ° kcal/mol 298 K1000 K CH 2 =CH 2 16.2828.25 CH 3 -CH 3 -7.8726.13 CH 3 CH 2 NH 2 8.9160.96 CH 3 CH 2 OH -40.22 1.98 NH 3 -3.8614.85 H 2 O -54.64 -46.04 H 2 0 0 N 2 0 0 ΔG reaction = ΣΔG f ° products - ΣΔG f ° reactants ΔG 298 = -1.65 kcal/mol ΔG 1000 = -1.91 kcal/mol ΔG 298 = + 16.78 kcal/mol ΔG 1000 = + 34.83 kcal/mol

18. Question: Under what conditions would the following reaction be the most promising? ΔG 298 = - 3.51 kcal/mol ΔG 1000 = + 17.86 kcal/mol Temperature? Pressure? Stoichiometry?

19. Other Considerations Evaluate: number of possible side-products (and separation difficulties) air or moisture sensitivity of reactants and intermediates commercial value of side-products environmental impact of side-products health and safety issues