Nerve agent

Diffusivity of Water versus Sarin in Air at 10 Degrees Celsius (50 Degrees Fahrenheit) and 1 Atmosphere[see bottom of post]

1991 Gulf War veterans are suffering from 1991 Gulf War Illness[3;References]. Scientific research suggests the combination of experimental medication, pyridostigmine bromide as an example, over use of pesticides, chemical weapon-sarin as an example-destruction at plants and football sized bunkers, oil fires, etc as the potential cause[6-9].

Dr. Robert Haley, MD, UT SouthWestern Medical Center, and Intelligence Analyst James Tuite have reported how 1991 Gulf War veterans might have been contaminated with chemical weapons prior to the ground war, “Desert Storm”[9]. In fact, their work provides data proving that sophisticated equipment detected chemical weapons in Saudi Arabia prior to the ground war[9a]. It is also hypothesized that the “toxic cocktail” has caused autonomic dysfunction, nerve death, and brain death[9-14].

As a 1991 Gulf War veteran, I have been affected. I am also a chemical engineer with a degree in biological sciences. Like most educated, I have lost much of my knowledge in chemical engineering and biological sciences, but I can, if I find a good example, still “plug and chug” by using “tested and trusted” equations, which is advised anyhow. 🙂 Here, I compare the diffusivity of sarin vapor and water vapor in air by using Chapman and Enskog equation with Brokaw relations for polar gases correction. I have shown that the equation can be used when considering the diffusivity of polar in a non-polar matrix[19]. After performing the latter calculation, I noticed that reference [1] also suggests Brokaw relations to be used for diffusivity of one polar gas molecule in a non-polar matrix[1].

I will be comparing the diffusivity of polar sarin = A in non-polar air = B at 10 $\textdegree$ C and 1 atmosphere. I chose 10 $\textdegree$ C because I discovered data, possibly experimental, that stated that 90% volume of 1 mm sarin drop on a non-absorbable surface at 10 $\textdegree$ C evaporated in 0.24 hours[17].

Equations

Chapman and Enskog Equation[1]. Reference [1] reports that this equation has a “Average absolute error” of 7.9% when used without Brokaw relations. The range is from 0% to 25%. The authors[1] did not provide an average for Browkaw relations but do provide specific absolute error values. When I averaged the Brokaw values[1], I obtained a 10.9% average absolute error with a range from 0% to 33%.

Chapman and Enskog Equation[1]

$D_{AB} = \frac{3}{16} \frac{(\frac{4 \pi \kappa T}{M_{AB}})^{1/2}}{n \pi \sigma_{AB}^2 \Omega_D} f_D$

Neufield, et al. Equation

$\Omega_D = \frac{A}{(T^*)^B} + \frac{C}{\exp{((D)(T^*))}} + \frac{E}{\exp{((F)(T^*))}} + \frac{G}{((H)(T^*))}$

Polar Gases: Brokaw Relations

$\Omega_D(Neufield) + \frac{0.19 \delta_{AB}^2}{T^*}$

$T^* = \frac{\kappa T}{\epsilon_{AB}}$

$\delta = \frac{1.94x10^3 \mu_p^2}{V_bT_b}$

$\mu_p = dipole \ moment, \ debyes$

$V_b = liquid \ molar \ volume \ at \ the \ normal \ boiling \ point, \ \frac{cm^3}{mol}$

$T_b = normal \ boiling \ point \ (1 \ atm), K$

$\frac{epsilon}{\kappa} = 1.18(1 + 1.3\delta^2)T_b$

$\sigma = (\frac{1.585V_b}{1 + 1.3 \delta^2})^{1/3}$

$\delta_{AB} = (\delta_A \delta_B)^{1/2}$

$\frac{\epsilon_{AB}}{\kappa} = (\frac{\epsilon_A}{\kappa} \frac{\epsilon_B}{\kappa})^{1/2}$

$\sigma_{AB} = (\sigma_A \sigma_B)^{1/2}$

When $f_D$ is chosen as unity and “n” is expressed by the ideal-gas law, the Chapman-Enskog Equation

$D_{AB} = \frac{0.00266 T^{3/2}}{PM_{AB}^{1/2} \sigma_{AB}^2 \Omega_D}$

Brokaw Diffusivity: Water in Air at 10 $\textdegree$ C and 1 Atmosphere

Molecular Weight

Water:

$M_A = M_{H_2O} = 2(MW_H) + 1(MW_O) = 2(1.008) + 1(16.00) = 18 \frac{g}{mol}$

Air: 1 mole basis

$21\% \frac{molO_2}{mol} \ O_2 \ and \ 79\% \frac{molN_2}{mol}\ N_2$

$Moles \ O_2 = 0.21 \frac{molO_2}{mole}(1 \ mol) = 0.21 \ molO_2; Moles \ N_2 = 0.79 \frac{molN_2}{mol} (1 \ mol) = 0.79 \ molN_2$

Grams oxygen:

$0.21 \ molO_2(MW_{O_2}) = 0.21 molO_2(\frac{32 \ grams \ O_2}{mol \ O_2}) = 6.72 \ grams \ O_2$

Grams nitrogen:

$0.79 \ molN_2(MW_{N_2}) = 0.21 molO_2(\frac{ 28 \ grams \ N_2}{mol \ O_2}) = 22.12 \ grams \ N_2$

Air: $M_B = M_{air} = \frac{(6.72 + 22.12)}{1mol} = 28.8 \frac{g}{mol}$

$M_{AB} = 2[\frac{1}{M_A} + \frac{1}{M_B}]^{-1} = 2[\frac{1}{18} + \frac{1}{28.8}]^{-1} = 22.2$

Need: $\sigma; \delta; \Omega_D$

Note: I will only be calculating a delta value for water because air is non-polar[1;19].

$\delta_A = \delta_{H_2O} = \frac{1.94x10^3 \mu_p^2}{V_bT_b}$

From [16]: $V_b \frac{cm^3}{mol} = 18.045 \frac{cm^3}{mol}$

From [20]: $\mu_{p_{H_2O}} = 1.855$

$T_b = 373 K$

$\delta_{A_{H_2O}} = \frac{1.94x10^3(1.855)^2}{(18.045)(373)} = \frac{6.68x10^3}{6.73x10^3} = 0.992$

$\frac{\epsilon_{A}}{\kappa} = 1.18(1 + 1.3 \delta_{A}^2)T_b = 1.18(1 + 1.3(0.992)^2)373 K = 1003 K$

$\sigma_A = (\frac{1.585V_b}{1 + 1.3\delta_A^2})^{1/3} = (\frac{1.585 (18.045)}{1 + 1.3(0.992)^2})^{1/3} = (12.55)^{1/3} = 2.32 \AA$

Need $T^*$ to calculate $\Omega_D$

$T^* = \frac{\kappa T}{\epsilon_{AB}}$

$\frac{\epsilon_{AB}}{\kappa} = (\frac{\epsilon_A}{\kappa} \frac{\epsilon_B}{\kappa})^{1/2}$

Water: $\frac{\epsilon_A}{\kappa} = 1003 K; Air[1, Appendix B]:78.6 K$

$\frac{\epsilon_{AB}}{\kappa} = \sqrt{\frac{\epsilon_A}{\kappa} \frac{\epsilon_B}{\kappa}} = \sqrt{(1003 K)(78.6 K)} = 280.8 K$

$T^* = \frac{\kappa T}{\epsilon_{AB}}$

$\frac{\epsilon_{AB}}{\kappa T} = \frac{280.8 K}{283 K} = 0.992$

$T^* = \frac{\kappa T}{\epsilon_{AB}} = \frac{1}{0.992} = 1.01$

Neufield, et al.:

$\Omega_D = \frac{A}{(T^*)^B} + \frac{C}{\exp{((D)(T^*))}} + \frac{E}{\exp{((F)(T^*))}} + \frac{G}{\exp((H)(T^*))} =$

$\Omega_D = \frac{1.06036}{1.01^{0.15610}} + \frac{0.19300}{\exp{((0.47635)(1.01))}} + \frac{1.03587}{\exp{((1.52996)(1.01))}} + \frac{1.76474}{\exp{((3.89411)(1.01))}} =$

$\Omega_D = 1.43$

$\Omega_D = \Omega_D(Neufield) + \frac{0.19 \delta_{AB}^2}{T^*}$ changed to $\Omega_D(Neufield) + \frac{0.19 \delta_A^2}{T^*}$

$\Omega_D = 1.43 + \frac{0.19(0.992)^2}{1.01} = 1.62$

Need $\sigma_{AB} = \sqrt{\sigma_A \sigma_B}$

Water: 2.32 $\AA$ ; Air (Appendix B[1]): 3.711 $\AA$

$\sigma_{AB} = \sqrt{\sigma_A \sigma_B} = \sqrt{(2.32)(3.711)} = 2.93 \AA$

Diffusivity: Polar water in non-polar air at 10 $\textdegree$ C and 1 atmosphere

$D_{AB} = \frac{0.00266 T^{3/2}}{PM_{AB}^{1/2} \sigma_{AB}^2 \Omega_D} = \frac{0.00266 (283)^{3/2}}{1 (22.2)^{1/2} (2.93)^2 (1.62)} = \frac{12.66}{65.53} =$

$D_{AB} = 0.193 \frac{cm^2}{s}$

Brokaw Diffusivity of Sarin in Air at 10 $\textdegree$ C and 1 Atmosphere

Molecular Weight

Sarin, $C_4H_{10}FO_2P$ :

$M_A = M_{C_4H_{10}FO_2P} = 4(MW_C) + 10(MW_H) + 1(MW_F) + 2(MW_O) + 1(MW_P) =$

$M_{C_4H_{10}FO_2P} = 4(12.01) + 10(1.008) + 1(19.00) + 2(16.00) + 1(30.97) = 140.1 \frac{g}{mol}$

Air: 1 mole basis

$21\% \frac{molO_2}{mol} \ and \ 79\% \frac{molN_2}{mol}$

0.21 $\frac{molO_2}{mol}$ (1 mol) = 0.21 mol oxygen gas; 0.79 $\frac{molN_2}{mol}$ (1 mol) = 0.79 mol nitrogen gas

Grams oxygen:

$0.21 (molO_2)(32 \frac{gO_2}{molO_2}) = 6.72 grams \ O_2$

Grams nitrogen:

$0.79 (molN_2)(28 \frac{gN_2}{molN_2}) = 22.1 grams \ N_2$

Air: $M_B = M_{air} = \frac{(6.72 + 22.12)}{1 mol} = 28.8 \frac{g}{mol}$

$M_{AB} = 2[\frac{1}{140.1} + \frac{1}{29.0}]^{-1} = 48.1$

Need: $\delta; \sigma; \Omega_D$

Note: I will only be calculating the delta value for the polar gas sarin because air is non-polar[1;19].

$\Omega_D = \Omega_D(Neufield) + \frac{0.19 \delta_{AB}^2}{T^*}$ changed to $\Omega_D(Neufield) + \frac{0.19 \delta_A^2}{T^*}$

$T^* = \frac{\kappa T}{\epsilon_{AB}}$

$\frac{\epsilon_i}{\kappa} = 1.18(1 + 1.3\delta_i^2)T_b$

Sarin: $\frac{\epsilon_A}{\kappa} = 1.18(1 + 1.3(0.418)^2)(420) = 608.2 K$

$\frac{\epsilon_{AB}}{\kappa} = (\frac{\epsilon_A}{\kappa} \frac{\epsilon_B}{\kappa})^{1/2}$

Sarin: $\frac{\epsilon_A}{\kappa} = 608.2 K$

Air[Appendix B;1]: $\frac{\epsilon_B}{\kappa} = 78.6 K$

$\frac{\epsilon_{AB}}{\kappa} = \sqrt{\frac{\epsilon_A}{\kappa} \frac{\epsilon_B}{\kappa}} = \sqrt{(608.2)(78.6)} = 216.1 K$

$T^* = \frac{\kappa T}{\epsilon_{AB}}$

$\frac{\epsilon_{AB}}{\kappa T} = \frac{216.1}{283} = 0.764$

$T^* = \frac{\kappa T}{\epsilon_{AB}} = \frac{1}{0.764} =1.31$

$\delta_A = \frac{1.94x10^3 \mu_p^2}{V_bT_b}$

$\mu_p =$ dipole moment, debyes

$V_b =$ liquid molar volume at the normal boiling point, $\frac{cm^3}{mol}$

$T_b =$ normal boiling point (1 atm), K

Sarin[18;16a]: $\delta_A = \frac{1.94x10^3(3.44)^2}{(130.9)(420)} = 0.418$

$\sigma_i = (\frac{1.585V_b}{1 + 1.3\delta_i^2})^{1/3}$

Sarin[16a]: $\sigma_A = (\frac{1.585(130.9)}{1 + 1.3(0.418)^2})^{1/3} = 5.5 \AA$

$\sigma_{AB} = (\sigma_A \sigma_B)^{1/2}$

Sarin: $\sigma_A = 5.5 \AA$

Air[Appendix B;1}: $\sigma_B = 3.711 \AA$

$\sigma_{AB} = \sqrt{(\sigma_A)(\sigma_B)}= \sqrt{(5.5)(3.711)} = 4.52 \AA$

$\Omega_D = \frac{A}{(T^*)^B} + \frac{C}{\exp{((D)(T^*))}} + \frac{E}{\exp{((F)(T^*))}} + \frac{G}{\exp{((H)(T^*))}} =$

$\Omega_D = \frac{1.06036}{(1.31)^{0.15610}} + \frac{0.19300}{\exp{((0.47635)(1.31))}} + \frac{1.03587}{\exp{((1.52996)(1.31))}} + \frac{1.76474}{\exp{((3.89411)(1.31))}} =$

$\Omega_D = 1.24$

$\Omega_D = \Omega_D(Neufield) + \frac{0.19 \delta_A^2}{T^*} = 1.24 + \frac{0.19(0.418)^2}{1.31} = 1.27$

Chapman-Enskog equation after polar correction

Diffusivity of Sarin in Air:

$D_{AB} = \frac{0.00266T^{3/2}}{PM_{AB}^{1/2}\sigma_{AB}^2 \Omega_D} = \frac{0.00266(283)^{3/2}}{1(48.1)^{1/2}(4.52)^2(1.27)} = \frac{12.66}{180.0} = 0.070 \frac{cm^2}{s}$

Diffusivity Comparison in Air: Water Versus Sarin in Descending Order

Water: $D_{AB} = 0.193 \frac{cm^2}{sec}$

Sarin: $D_{AB} = 0.070 \frac{cm^2}{sec}$

Diffusivity Ratio: $\frac{Water}{Sarin} = \frac{0.193}{0.070} = 2.74$

References:

[1] Poling, Bruce E.; Prausnitz, John M.; O’Connell, John P. (2001) The Properties of Gases and Liquids, Fifth Edition. New York: Mcgraw-Hill.

[2] Welty, James R.; Wicks, Charles E.; Wilson, Robert E. (1984) Fundamentals of Momentum, Heat, and Mass Transfer, third edition. New York: John Wiley & Sons.

[3] Harding, Byron. 1991 Gulf War Illnesses and Differing Hypotheses: Nerve and Brain Death Versus Stress, December 2012. gather.com[online] 2012. Available from: http://www.gather.com/viewArticle.action?articleId=281474981824775

[4] Removed

[4a] Removed

[5] National Academies.News.Gulf War Service Linked to Post-traumatic Stress Disorder, Multisymptom Illness, Health Problems, But Causes Unclear. nationalacademies.org[online].April 2010. Available from: http://www8.nationalacademies.org/onpinews/newsitem.aspx?RecordID=12835

[6] National Academies Press. Institute of Medicine. Committee on Gulf War and Health: Health Effects of Serving in the Gulf War, Update 2009. Board on Health of Select Populations. Gulf War and Health, Volume 8. nap.edu[online]. 2010. pp. 320. Available from: http://www.nap.edu/catalog.php?record_id=12835 ISBN-10: 0-309-14921-5; ISBN-13: 978-0-309-14921-1

[7] Research Advisory Committee on Gulf War Veterans’ Illnesses. Gulf War Illness and Health of Gulf War Veterans. Scientific Findings and Recommendations, 2008. va.gov[online]. 2012. Available from: http://www.va.gov/RAC-GWVI/docs/Committee_Documents/GWIandHealthofGWVeterans_RAC-GWVIReport_2008.pdf

[8] Research Advisory Committee on Gulf War Veterans’ Illnesses. Research Advisory Committee on Gulf War Veterans’ Illnesses Findings and Recommendation, June 2012. va.gov[online]. 2012. Available from: http://www.va.gov/RAC-GWVI/docs/Committee_Documents/CommitteeDocJune2012.pdf

[9] Kennedy, Kelly. Study: Wind blew deadly gas to U.S. troops in Gulf War, December 2012. ustoday.com[online]. 2012. Available from: http://www.usatoday.com/story/news/world/2012/12/13/sarin-gas-gulf-war-veterans/1766835/

[9a] Haley, Robert W.; Tuite, James J. Meteorological and Intelligence Evidence of Long-Distance Transit of Chemical Weapons Fallout from Bombing Early in the 1991 Persian Gulf War, December 2012. karger.com[online]. 2012. vol. 40. pp. 160-177. Available from: http://content.karger.com/ProdukteDB/produkte.asp?Aktion=ShowFulltext&ArtikelNr=345123&Ausgabe=257603&ProduktNr=224263 DOI: 10.1159/000345123

[9b] Haley, Robert W.; Tuite, James J. Epidemiologic Evidence of Health Effects from Long-Distance Transit of Chemical Weapons Fallout from Bombing Early in the 1991 Persian Gulf War, December 2012. karger.com[online]. vol. 40. pp. 178-189. Available from: http://content.karger.com/ProdukteDB/produkte.asp?Aktion=ShowFulltext&ArtikelNr=345124&Ausgabe=257603&ProduktNr=224263 DOI: 10.1159/000345124

[10] Oswal, DP; Garrett, TL; Morris, M; Kucot, JB. Low-dose sarin exposure produces long term changes in brain neurochemistry of mice. Neurochem Res[online]. 2013. vol. 1. pp. 108-116. Available from: http://www.ncbi.nlm.nih.gov/pubmed/23054072 doi: 10.1007/s11064-012-0896-9

[11] Shewale, SV.; Anstadt, MP; Horenziak, M; Izu, B.; Morgan, EE.; Lucot, JB.; Morris, M. Sarin causes autonomic imbalance and cardiomyopathy: an important issue for military and civilian health, July 2012. J. Cardiovasc Pharmacol.[online]. 2012. vol 60(1). pp. 76-87. Available from: http://www.ncbi.nlm.nih.gov/pubmed/22549449 doi: 10.1097/FJC.0b013e3182580b75

[12] DTIC. Online Information for the Defense Community.Chan, Victor T; Soto, Armando; Wagner, Jessica A; Watts, Brandy S.; Walters, Amy D.; Hill, Tiffany M. Mechanisms of Organophosphates (OP) Injury: Sarin-Induced Hippocampal Gene Expression Changes and Pathway Perturbation, Jan 2012. dtic.mil[online]. 2012. Available from: http://www.dtic.mil/docs/citations/ADA560343

[13] Medical News Today. Low-Level Exposure to Organophosphate Pesticides Damage Brain and Nervous System, December 2012. medicalnewstoday.com[online]. 2012. Available from: http://www.medicalnewstoday.com/releases/253534.php

[14] Fulco, Carolyn E; Liverman, Catharyn T.; Sox, Harold C. National Academy Press. Committee on Health Effects Associated with Exposures During the Gulf War. Gulf War and Health: Volume 1. Depleted Uranium, Sarin, Pysidostigmine Bromide, Vaccines, 2000. Effects of Long-Term Exposure to Organophosphate Pesticides in Humans. nap.edu[online]. 2012. Available from: http://www.nap.edu/openbook.php?record_id=9953&page=R1

[15] NCBI.PubChem. Sarin-Compound Summary (CID 7871). pubmed.ncbi.nlm.nih.gov[online]. 2012. Available from: http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=7871

[16] ChemSpider. The free chemical database. Water. chemspider.com[online]. 2013. Available from: http://www.chemspider.com/Chemical-Structure.937.html?rid=01a81689-c122-434f-a0a1-b4e6e3ca8109

[16a] ChemSpider. The free chemical database. Sarin (isopropyl methylphosphonofluoridate). chemspider.com[online]. 2013. Available from: http://www.chemspider.com/Chemical-Structure.7583.html?rid=8885b92c-43db-4dbf-a9fd-280d32df0450

[17] US National Library of Medicine. WISER: Wireless Information System for Emergencey Responders. Sarin, CAS RN: 107-44-8. Volatilization. webwiser.nlm.nih.gov[online]. 2012. Available from: http://webwiser.nlm.nih.gov/getSubstanceData.do;jsessionid=E6C28B95977867F872631D36CDD61D42?substanceID=151&displaySubstanceName=Sarin&UNNAID=&STCCID=&selectedDataMenuItemID=81

[18] Lee, Ming-Tsung; Vishnyakov, Aleksey; Gor, Gennady Yo.; Neimark, Alexander V. Interactions of Phosphororganic Agents with Water and Components of Polyelectrolyte Membranes, October 2011. J. Physical Chemistry[online]. 2012. Available from: http://www.princeton.edu/~ggor/Gor_JPCB_2011.pdf

[19] Harding, Byron. Chapman and Enskog Versus Hirschfelder Equation when Compared to Experimental Value at 25 Degree C and 1 Atm, and Non-Polar Versus Brokaw Polar Method, January 2013. Available from: https://chrisbharding.wordpress.com/2013/01/04/chapman-and-enskog-versus-hirschfelder-equation-and-compared-to-experimental-value-at-25c-and-1-atm/

[20] Gregory, J.K.; Clary, D.C.; Liu, K.; Brown, M.G.; Saykally, R.J. The Water Dipole Moment in Water Clusters, February 1997. science[online]. vol. 275. pp. 814. Available from: http://www.cchem.berkeley.edu/rjsgrp/publications/papers/1997/187_gregory_1997.pdf

An Experiment In Life

Chemical Engineering, Biological Sciences, and 100% Veteran's Disability,

Diffusivity of Water versus Sarin (Nerve Agent) in Air at 10 Degrees Celsius (50 Degrees Fahrenheit) and 1 Atmosphere