Designing Chemical Products. Dr. Kevin G. Joback Molecular Knowledge Systems, Inc.

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1 Designing Chemical Products Dr. Kevin G. Joback

{1} O C O O O C O CH2 CH2 {1} {1} C C O CH2 CH2 O {1} Group -CH3 -OH >C=O Intercept O SP,p -0.591-0.377 5.548 4.670 4.729 5.067 SP,h -0.848-0.595 10.630 4.846 4.012 7.

2 {1} O C O O O C O CH2 CH2 {1} {1} C C O CH2 CH2 O {1} Group -CH3 -OH >C=O Intercept O SP,p SP,h P = CH 3 RT V b Z OH CH P CH 2 CH 3 1 = a V ( V + b) + b( V b) + B V + RT V b C V + a 2 V Density Viscosity Solubility Melt Point Flash Point {1} O C O O O # Carbons O C O CH2 CH2 {1} {1} C C O CH2 CH2 O {1} # Carbons A + B B Liquid & Solid wt% Depressant SP, Hydrogen Bonding A + S -CH3 S A Group -CH3 -OH >C=O -COO- Slope = CH2- -COO- -CH2- -CH2- Slope = CH2- -CH2- -COO- -CH2- -COO- Intercept Liquid & Solid SP,p SP,h wt% Depressant O {1} O C O O O C O CH2 CH2 {1} {1} C C O CH2 CH2 O {1} Group -CH3 -OH >C=O Intercept SP,p SP,h P = CH 3 RT V b Z OH CH P CH 2 CH 3 1 = a V ( V + b) + b( V b) + B V + RT V b C V + a 2 V Density Viscosity Solubility Melt Point Flash Point O {1} O C O O # Carbons O C O CH2 CH2 {1} {1} C C O CH2 CH2 O {1} # Carbons A + B B Liquid & Solid wt% Depressant -CH3 SP, Hydrogen Bonding A + S S A Group -CH3 -OH >C=O Slope = CH2- -COO- -CH2- -CH2- Slope = CH2- -CH2- -COO- -CH2- Intercept Liquid & Solid SP,p SP,h wt% Depressant Molecular Knowledge Systems Located in New Hampshire, USA Company Started in 1989 Computer Software Consulting Equations of State Group Contributions Phase Equilibrium = 2 Boiling Point, K Temperature, C Substructure Search Estimate Properties Substructure Search Design Chemical Products Group Contributions T b = Σ n i i SP, Polar Equations of State Group Contributions Phase Equilibrium Substructure Search = 2 Estimate Properties Boiling Point, K Substructure Search Temperature, C Design Chemical Products Group Contributions Group Contributions Formulate Mixtures 15% 20% 31% 34% Boiling Point, K Group Contributions Select Solvents Temperature, C Phase Equilibrium Group Contributions T b = Σ n i i Formulate Mixtures 15% 20% 31% 34% Boiling Point, K Group Contributions SP, Polar Select Solvents Temperature, C Phase Equilibrium SYNAPSE info@molecularknowledge.com CRANIUM info@molecularknowledge.com Emulsifier Phase Oxygen Carrier Continuous Phase Page 2

3 Designing Chemical Products Some example projects we have worked on Artificial Blood Refrigeration Lubes Degreasing Solvents Non-MMH Rocket Fuels Aircraft Deicing Fluids Soil Consolidants Sonar Fill Fluids Phase Change Materials CO2 Absorption Solvents Hydraulic Energy Storage Windshield Washer Fluid Pour Point Depressant Page 3

4 Our Core Knowledge Thermal Conductivity Liquid Viscosity Surface Tension Heat Capacities Vapor Pressure Liquid Density Flash Point Structure Property Relationships Page 4

candidate structures and mixtures 3) Testing if

5 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Experimental Approach Good Solvent Page 5

6 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 6

7 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 7

8 Step 1: Identify Constraints Do not focus on chemicals or ingredients. Focus on physical properties. People don t need drills. People need holes. - Basic Marketing People don t need chemicals. People need the properties those chemicals possess. - Kevin G. Joback Page 8

9 Example: Windshield Washer Fluid US Patent 07,585,828 Example Formulation Why are these ingredients in this product? Ingredient 1. Methanol (solvent) 2. Chromatech Yellow 3. XD-56 Antifoam 4. Formasil Water Weight % Page 9

10 Example: Windshield Washer Fluid Focus on physical properties Surface Tension Wetting Phase Equilibria Solubility Phase Equilibria Evaporation Viscosity Fluid Flow Density Fluid Flow Phase Equilibria Non-solubility Reactivity Corrosion Phase Equilibria Low Freezing Point Light Absorption Color Safety Low Flammability Safety Toxicity Page 10

Step 1: Identify Constraints The required physical properties place constraints on the molecular structure of the solvent 1. Non-reactive with metal no -COOH group 2.

11 Step 1: Identify Constraints The required physical properties place constraints on the molecular structure of the solvent 1. Non-reactive with metal no -COOH group 2. Environmentally friendly no Cl, -F, -Br 3. Must wet glass surface hydrocarbon 4. Rapid evaporation rate low Mw 5. Low freezing point -OH group 6. Low flammability -OH, -Cl, -F 7. Low toxicity water soluble 8. Low viscosity low Mw Page 11

Example: Ball Point Pen Ink US Patent 05,466,281 Example Formulation Why are these ingredients in this product? Ingredient 1. Sunsperse black LHD-9303 2.

12 Example: Ball Point Pen Ink US Patent 05,466,281 Example Formulation Why are these ingredients in this product? Ingredient 1. Sunsperse black LHD Ammonia as 20% NH3 3. Cobratec TT-25-EG 4. Ethylene glycol 5. Surfynol 104E 6. Xanthan gum 7. Proxel GXL 8. Joncryl 58 Weight % Page 12

13 Example: Ball Point Pen Ink Important Physical Properties Viscosity - Suspension Density Fluid Flow Reactivity Corrosion Phase Equilibria Drying Surface Tension Adhesion Light Absorption Color Glass Transition Temp Film Forming Young s Modulus Stress Strain Surface Tension Wetting Page 13

14 Step 1: Identify Constraints The required physical properties place constraints on the mixture s ingredients 1. Non-reactive with metal corrosion inhibitor 2. Must suspend pigment particles thickener 3. Must not degrade for many years biocide 4. Must adhere particles to paper polymer 5. Rapid evaporation rate low Mw solvent 6. Shear thinning viscosity thickener 7. Must wet paper surface surfactant 8. Must form a tough film polymer Page 14

15 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 15

16 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 16

17 Designing Chemical Products Generating Candidates Pure Components and Mixtures 1) Generating Structures: the molecular structure of pure component candidates 2) Generating Mixtures: the components and concentration of mixture candidates Page 17

18 Designing Chemical Products Generating Candidates Pure Components and Mixtures 1) Generating Structures: the molecular structure of pure component candidates 2) Generating Mixtures: the components and concentration of mixture candidates Page 18

19 Step 2: Generating Structures Groups are small pieces of molecular structure. Begin by compiling groups. CH 3 CH 2 >CH COO OH CO NH 2 NH >N O -Br F Cl COOH SH Page 19

20 Step 2: Generating Structures Eliminate groups based on reactivity, corrosivity, odor, safety,... CH 3 CH 2 >CH COO OH CO NH 2 NH >N O -Br F Cl COOH SH Page 20

21 Step 2: Generating Structures Exhaustively generate all combinations. Combinations of 2 groups, 3 groups, 2 Groups -CH 3 -CH 3 -CH 3 -CH 2 - -CH 3 >CH- -CH 3 -OH -CH 3 -NH- -CH 3 >N- 3 Groups -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 2 - -CH 3 -CH 3 >CH- -CH 3 -CH 3 -OH -CH 3 -CH 3 -NH- -CH 3 -CH 3 >N- 4 Groups -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH2- -CH 3 -CH 3 -CH 3 >CH- -CH 3 -CH 3 -CH 3 -OH -CH 3 -CH 3 -CH 3 -NH- -CH 3 -CH 3 -CH 3 >N- Page 21

22 Step 2: Generating Structures Delete infeasible combinations. Feasible combinations must satisfy: b = number of bonds n = number of groups r = number of rings -CH 3 -CH 3 -CH 3 -CH3 b = 4 n = 4 r = 0 Page 22

23 Step 2: Generating Structures Delete infeasible combinations. Feasible combinations must satisfy: -CH 3 -CH 3 -CH 3 >Nb = 6 n = 4 r = 0 b = number of bonds n = number of groups r = number of rings CH 3 -N-CH 3 CH 3 Page 23

24 Step 2: Generating Structures Delete infeasible combinations. b/2 = n 1 + r 2 Groups -CH 3 -CH 3 -CH 3 -CH 2 - -CH 3 >CH- -CH 3 -OH -CH 3 -NH- -CH 3 >N- 3 Groups -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 2 - -CH 3 -CH 3 >CH- -CH 3 -CH 3 -OH -CH 3 -CH 3 -NH- -CH 3 -CH 3 >N- 4 Groups -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH 3 -CH2- -CH 3 -CH 3 -CH 3 >CH- -CH 3 -CH 3 -CH 3 -OH -CH 3 -CH 3 -CH 3 -NH- -CH 3 -CH 3 -CH 3 >N- Page 24

25 Step 2: Generating Structures Groups must now be connected. Enumeration of all bonds -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- Page 25

26 Step 2: Generating Structures Eliminate infeasible bonds Eliminate duplicate structures -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- Page 26

27 Step 2: Generating Structures Eliminate infeasible bonds Eliminate duplicate structures -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- Page 27

28 Step 2: Generating Structures Repeat the procedure for each bonded substructure -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- -NH-OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - Page 28

29 Step 2: Generating Structures Finally we have enumerated all candidate molecular structures -OH -OH -CH 2 - -CH 2 - -CH 2 - -CH 2 - -NH- HO-CH 2 -CH 2 -CH 2 -CH 2 -NH-OH HO-CH 2 -CH 2 -CH 2 -NH-CH 2 -OH HO-CH 2 -CH 2 -NH-CH 2 -CH 2 -OH Page 29

30 Designing Chemical Products Generating Candidates Pure Components and Mixtures 1) Generating Structures: the molecular structure of pure component candidates 2) Generating Mixtures: the components and concentration of mixture candidates Page 30

31 Step 2: Generating Mixtures Begin by collecting chemicals into component categories Category: Solvent 1 Propylene glycol Isopropanol Methanol Glycerol Ethanol Category: Solvent 2 Propylene glycol Isopropanol Methanol Glycerol Ethanol Category: Water Water Page 31

32 Step 2: Generating Mixtures Specify each category s concentration: minimum, maximum and increment Category Min, wt% Max, wt% Increment Solvent Solvent Surfactant Colorant Water q.s. q.s. = quantum sufficit (amount needed) Page 32

33 Step 2: Generating Mixtures First all concentrations are generated for the component categories Candidate 0001 Solvent Solvent Surfactant Colorant Water Candidate 0002 Solvent Solvent Surfactant Colorant Water Candidate 0253 Solvent Solvent Surfactant Colorant Water Constraint: concentration must total 100% Page 33

34 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 34

35 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 35

36 Step 3: Evaluating Candidates Three Main Categories of Property Estimation Techniques Group Contribution Techniques Equation Oriented Techniques Mixture Estimation Techniques Page 36

37 Step 3: Evaluating Candidates Three Main Categories of Property Estimation Techniques Group Contribution Techniques Equation Oriented Techniques Mixture Estimation Techniques Page 37

38 Group Contribution Techniques 800 Normal Paraffins Homologous 1 Series Boiling Point [K] Slope = 22.9 CH 3 CH 2 CH 3 n Contribution -CH2- = Number of Carbons Page 38

39 Group Contribution Techniques OH CH CH 3 2 Group -CH3 -CH3 1 Tb CH 2 -CH CH 3 >CH- -OH ) Select Technique 2) Dissect Structure 3) Get Contributions 4) Insert into Model Tb (est) K Tb (lit) K Tb = Σ i 4 Page 39

40 Boiling Point, Estimation Errors Statistics 70 Observations Avg Error 0.97 K 50 Avg Abs Err 15.1 K Percentage Avg % Error Max Error Outliers, Errors 4.8 % K (Estimate Data) [K] Estimates generated using Joback s method N-Methylformamide Acetamide Fluorine Cyanogen K K K K Page 40

41 Step 3: Evaluating Candidates Three Main Categories of Property Estimation Techniques Group Contribution Techniques Equation Oriented Techniques Mixture Estimation Techniques Page 41

42 Equation Oriented Techniques Vapor Pressure - Heptane Pvp ln( P c ) 1 ln = T br 1 Pc 1 Tbr Tr Required Properties Tc Critical Temperature Pc Critical Pressure Vapor Pressure [MPa] Tb Boiling point Temperature [K] Page 42

43 Step 3: Evaluating Candidates Three Main Categories of Property Estimation Techniques Group Contribution Techniques Equation Oriented Techniques Mixture Estimation Techniques Page 43

44 Mixture Techniques ( η ) = x ln( η ) x ln( ) ln η2 m + + x 1 x 2 G Mixture Functions Pure Data Inputs Reduces to Pure Liquid Viscosity [cp] Ethanol - Water Molecular Forces Characteristics Mole Fraction Ethanol Page 44

45 Example: CO 2 Absorption Solvent Absorption, Heat Exchange, Distillation to stack lean solvent added solvent CO 2 absorber stripper flue gas rich solvent Page 45

46 Example: CO 2 Absorption Solvent Absorber to stack lean solvent Packed Column: Percentage of packing wetted by the solvent is important Wilcox, Rochana, Kirchofer, Glatz and He. Energy and Environmental Science, volume 7, page 1769, flue gas rich solvent Page 46

47 Example: CO 2 Absorption Solvent Percentage of packing wetted by the solvent a t = total area a w = wetted area L = liquid velocity ρ = solvent density σ c = critical surface tension σ = solvent surface tension g = gravitational constant µ = solvent viscosity Page 47

48 Example: CO 2 Absorption Solvent For 30 wt% Monoethanolamine (MEA) in Water Temp = K σ c = N/m a t = 500 m 2 /m 3 L = m/s g = 9.81 m/s 2 µ = Pa s ρ = kg/m 3 σ = N/m Estimated values Page 48

49 Step 1: Identify Constraints A more extensive design would have constraints on the percentage of wetted surface area, the potential for flooding, the energy usage, and many more. For this example we simply create a constraint on the percentage of wetted surface area. Constraint: Better than MEA Page 49

50 Step 2: Generate Candidates We chose the following design groups -CH3 -CH2- >CH- >C< -OH -NH2 >NH >N- We chose a fixed amount of solvent in water: 30% Water Mixtures Page 50

51 Step 3: Evaluate Candidates T b = Joback s Technique (GCT) T c = Joback s Technique (GCT) P c = Joback s Technique (GCT) σ = Sastri + Rao Technique (EOT) µ = Joback s Technique (GCT) ρ = Rackett Equation (EOT) First estimates are generated. Estimates are then inserted into the wetting equation. Page 51

52 Step 3: Evaluate Candidates Mixtures: 30 wt% Candidate + 70 % Water µ = Arrhenius Equation (Mix) ρ = Weight Fraction Average (Mix) σ = Weight Fraction Average (Mix) Page 52

53 Step 3: Evaluate Candidates 2-Amino-2-methylpropanol Pure Component Ests µ = Pa s ρ = kg/m 3 σ = N/m Mixture Estimates µ = Pa s ρ = kg/m 3 σ = N/m Page 53

54 Interesting Candidates Some designed candidates and their a w /a t values Page 54

55 Designing Chemical Products Three Main Steps 1) Identifying physical property constraints 2) Generating candidate structures and mixtures 3) Testing if candidates satisfy constraints Computational Approach T b > 100 C T m < -40 C ρ > 1000 kg/m 3 CH 3 -O-CH 2 -CH 3 CH 3 -S-CH 2 -CH 3 CH 3 -NH 2 -CH 2 -CH 3 CH 3 -CO-CH 2 -CH 3 Σni i,tb Σn i i,tm Page 55

56 Designing Chemical Products Applicable to many types of chemical products Artificial Blood Refrigeration Lubes Degreasing Solvents Non-MMH Rocket Fuels Aircraft Deicing Fluids Soil Consolidants Sonar Fill Fluids Phase Change Materials CO2 Absorption Solvents Hydraulic Energy Storage Windshield Washer Fluid Pour Point Depressant Page 56

57 Thank You Thank you again for the opportunity to speak to you today. Questions? Page 57

Chemical Product Design How is it done? Dr. Kevin G. Joback Molecular Knowledge Systems, Inc.

Chemical Product Design How is it done? Dr. Kevin G. Joback kevin@molecularknowledge.com O O {1} O C C O CH2 CH2 {1} O O {1} C C O CH2 CH2 O {1} RT a P = V b V ( V + b) + b( V b) B C Z 1+ + + V V RT a