The Heat of Vaporization of Nicotine from Tobacco · The Heat of Vaporization of Nicotine from...

The Heat of Vaporization of Nicotine

from Tobacco

Kelley St.Charles 1, Serban Moldoveanu 2

1) Consultant to R.J. Reynolds Tobacco Company 2) R.J. Reynolds Tobacco Company, Winston-Salem, NC

1Tobacco Science Research Conference, Naples, FL, Sept. 20-23, 2015

Introduction

• Follow up to 2014 TSRC Paper*• Nicotine vapor pressure at 23 ºC measured• Pure nicotine and multiple tobacco types• Vapor pressure since measured at higher

temperatures

*K. St.Charles & S. Moldoveanu, Nicotine activity in tobacco. Paper # 40.

Introduction

Clausius-Clapeyron Equationln(P) = - ΔHvap /RT + C

P = Vapor Pressure (any pressure units)ΔHvap = Heat of vaporization* (J/mol)R = Gas Constant (8.314 J/K/mol)T = Absolute Temperature (K)C = Unitless constant

* Enthalpy of Vaporization or Sublimation

Experimental

Rearranged Clausius-Clapeyron Eqn.

ln(P) = (-ΔHvap/R) * 1/T + C

• Vapor P measured at 23, 30, 40 ºC• Linear regression of ln(P) versus 1/T• Slope = -ΔHvap/R• ΔHvap = - Slope * R

Experimental summary

• Details in 2014 presentation• Used pure nicotine and multiple tobacco types• Samples stored in Al-foil lined gas bags with septum• Diaphragm pump to sample 2 L headspace (HS) from

tobacco• 10 mL gas-tight syringe to sample pure nicotine HS• HS sampled through XAD-4 cartridge similar to ETS

nicotine• Pure nicotine HS also sampled directly in syringe

containing extraction solution

Experimental summary (cont.)

• Analysis by GC/MS/MS– Ethyl acetate solvent with 5000 ppm triethylamine– Deuterated nicotine (methyl -d3) internal standard– MRM Nicotine m/z 162 → 84 & m/z +3 for internal standard– 30 minute run time

• Calibration from 4.2 – 2140 ng/mL nicotine

• Signal to noise = 240 @ 8.3 ng/mL

Foil-lined gas bag modified• 1/8” stainless steel Swagelok® union replaced

Restek® polypropylene septum holder– Bulkhead union nut inside bag– PTFE lined septum replaced back ferrule outside bag

• Outer changed to Sorbent Systems bag– 5 mil (127 µm) thick, 4-layer film: PET/PE/Al foil/PE– ~20 x 25 cm (nicotine HS) & 40 x 50 cm (tobacco HS)

• Heavy-duty Al foil (~23.5 µm) inner liner– Added Al tape to reinforce foil at union penetration– Edges double folded and reinforced with Al tape– Tested heavier gauge foil with pure nicotine

Tobacco headspace sampling

Needle

XAD-4Cartridge

½ of size 6D Silicone Stopper

4.8 ID x 7.9 OD mm Tubing

4.8 x 7.9 mm Tubing

Tobacco types

Conditioned to water activity = 0.61Used 50+ g per bagBags filled with nitrogen

Results

Pure nicotine vapor pressure

XAD-4 = 62% of in-syringe sampling

Pure nicotine resultsIn-syringe comparison to published results

A. Harlan & Hixon. Ind Eng Chem. 1928, 20(7): 723–724.

B. Walker et al. Chem Senses. 1990, 15(2): 165-177

C. Norton et al. J Amer Chem Soc. 1940, 62: 261-264.

D. Boldridge & Kelly. 1988. Eqn. 6. http://legacy.library.ucsf.edu/tid/usx83d00/pdf

E. Johnson. 1990, Eqn. 2. http://legacy.library.ucsf.edu/tid/fma51f00/pdf

F. Banyasz. 1999. Eqn. 2. in: Analytical determination of nicotine and related compounds and their metabolites. p.153

Linear Regression ofln P vs 1/TR2 = 0.9995

ΔHvap = 56.6 kJ/mol

Ref A = 64.4 kJ/molRef D = 72.3 kJ/molRef E = 82.4 kJ/molRef F = 65.0 kJ/mol

Nicotine vapor from tobacco

*Activity = Vapor Pressure / Pure Nicotine Vapor Pressure

Nicotine vapor pressure

• Pure nicotine vapor pressure – 110 – 240 X > Burley

– 700 – 1100 X > Flue Cured

– 3200 – 7600 X > Oriental

• Vapor P Burley 6–10 X > Flue Cured 4-5 X > Oriental• Vapor P Cigarette blends ≥ Flue Cured• Tobacco nicotine activity slightly with temperature

(i.e. relative vapor pressure increases more than pure nicotine)

Nicotine activity in tobaccoUn-protonated calculated using:1. Tobacco % nicotine (DWB)2. Tobacco extract pH3. pKa as f(temperature)*

*Clayton et al. 2013, Anal. Methods, 81-88

Polynomial RegressionY = 14.12 X – 5542 X2

Intercept term not significant

R2 = 0.986Std. Error = 0.04% Activity

Heat of vaporization - ΔHvap

No obvious trends with respect to:– Tobacco origin, type, stalk position, or nicotine concentration– Wide range of nicotine activities

Combined heat of vaporization

• Mean ΔHvap = 86.7 kJ/mol, SD = 5.6 kJ/mol• 30 kJ/mol more endothermic than pure nicotine

– ΔH for mono-protonated → un-protonated nicotine reported as 34A & 41B kJ/mol*

– Property of nicotine rather than tobacco type

• Supports 2-step vaporization process from tobacco1. Dissociation of mono-protonated to un-protonated nicotine

2. Vaporization of un-protonated nicotine

A. Banyasz.1999 in: Analytical determination of nicotine and related compounds and their metabolites. p.159

B. Clayton et al. 2013, Anal. Methods, 81-88

Conclusions• Pure nicotine vapor P & ΔHvap similar to literature

(foil lined gas bags + in-syringe extraction)

• Pure nicotine vapor P 110 – 7600 X greater than that from tobacco

• Nicotine activity of Burley > Flue Cured > Oriental• Activity appears a function of un-protonated nicotine

concentration and temperature• Tobacco moisture can also influence nicotine activity

(Observed but not quantified).

Conclusions – ΔHvap from tobacco

• ΔHvap did not depend on tobacco origin, type, stalk position, nicotine concentration or activity

• ΔHvap depends on the nicotine properties rather than tobacco properties

• Mean ΔHvap = 86.7 kJ/mol, RSD = 6.5%• Supports 2-step vaporization process from tobacco

1. Dissociation of mono-protonated to un-protonated nicotine (~30 kJ/mol)

2. Vaporization of un-protonated nicotine (~57 kJ/mol)

Thanks to

• R.J. Reynolds Tobacco Company Research and Development

• You for listening

Questions ?21Tobacco Science Research Conference, Naples, FL, Sept. 20-23, 2015

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