Characteristics of the Chemical Industry

1) Basic objective - make a profit 2) Very competitive - there are hundreds of chemical companies, both small and very largethere 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

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 ! Europe 31% USA 28% Asia/Pacific 27% Other* 14% *Other: Latin America, non-E.U. Europe, Africa, Oceania, Canada

The Chemical Sector at a Glance

Worlds largest chemical producer : U.S.A. (Worlds largest chemical exporter : Germany)

North American Chemicals Output (2002): $505 Billion USD USA Canada Mexico 92% 5% 3% ($467 Billion USD) ($23 Billion USD) ($15 Billion USD)

Laboratory Chemistry vs. Industrial Chemistry 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.

Differences in the Synthetic Approach

e.g., formation of ethyl alcohol by hydration of ethylene:
H2C CH 2 + H2O H H3C H2 C OH

Laboratory Scale bubble ethylene into 98% H2SO4 dilute and warm the reaction mixture to hydrolyze the resultant sulfate ester Industrial Scale a stream of ethylene is mixed with steam at 325C 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.

Different Approaches for Different Objectives

Laboratory Objectives synthesize the product in the most convenient manner considering: 1) chemists time 2) equipment available (usually must use glassware) 3) conditions achievable (usually close to ambient pressure and between -195.8 C (N2(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

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.

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

1. 2. 3. CH 3CH 2Cl H3C C N CH 3CH 2NO2 O 4. H3C O 5. 6. 7. 8. H3C H + NH3 + NH3 + NH3 + 0.5 N2 + 0.5 H2 CH 3CH 2NH2 CH 3CH 2NH2 CH 3CH 2NH2 CH 3CH 2NH2 + 2 H2O + H2O H + NH2OH + 2 H2 CH 3CH 2NH2 + 2 H2O + 2 NH3 + 2 H2 + 3 H2 CH 3CH 2NH2 CH 3CH 2NH2 CH 3CH 2NH2 + 2 H2O + 2 NH4Cl

CH 3CH 2OH H2C CH 2 H3C CH 3

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.

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).

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 (G). GR = HR - T SR 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 Gf.

Greaction = Gfproducts - Gfreactants

Example: Dissociation of ethyl chloride

CH 3CH 2Cl
At 298 K
CH3CH2Cl H2C CH2 HCl

H2C CH 2

+ HCl

Hf Gf S

-26.70 -14.34 At 1000 K

12.50 16.28

-22.06 -22.77

Hf Gf S

-30.43 18.60 93.80

9.21 28.85 72.07

-22.56 -24.08 53.25

Hrxn = HfCH2=CH2 + HfHCl - HfCH3CH2Cl Grxn = GfCH2=CH2 + GfHCl - GfCH3CH2Cl Srxn = SCH2=CH2 + SHCl - SCH3CH2Cl

At 298 K: Hrxn = +17.14 kcal/mole Grxn = +7.86 kcal/mole Srxn = +31.15 cal/mole At 1000 K: Hrxn = +17.08 kcal/mole Grxn = -14.43 kcal/mole Srxn = +31.52 cal/mole Change in Free Energy -G small +G large +G

- G at 1000 K only!

Indication promising worth further investigation possible only under unusual conditions

Gf kcal/mol 298 K 1000 K

CH2=CH2 CH3-CH3 CH3CH2NH2 CH3CH2OH NH3 H2O H2 N2 16.28 -7.87 8.91 -40.22 -3.86 -54.64 0 0 28.25 26.13 60.96 1.98 14.85 -46.04 0 0

Greaction = Gfproducts - Gfreactants

H3C CH 3 + 0.5 N2 + 0.5 H2 CH 3CH 2NH2

G298 = + 16.78 kcal/mol G1000= + 34.83 kcal/mol G298 = -1.65 kcal/mol G1000= -1.91 kcal/mol

CH 3CH 2OH + NH3

CH 3CH 2NH2 + H2O

Question: Under what conditions would the following reaction be the most promising?
H2C CH 2 + NH3 CH 3CH 2NH2

G298 = - 3.51 kcal/mol G1000= + 17.86 kcal/mol Temperature?

Pressure?
Stoichiometry?

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