The Rest of the Story: Calculating Vapor Density

David F. Peterson

For many years Americans have enjoyed the news broadcasts and contemporary information that has been presented by Paul Harvey on the radio. In particular, one segment of his show that reveals very interesting facts is " he !est of the "tory". Harvey usually tells listeners much more behind the scene information than most people have heard on a certain topic. #sually, when the story is complete, the listener has a better understanding of why things are the way they are$the rest of the story, if you will. his same concept also applies to ha%ardous materials response in many ways. &ne topic where the rest of the story information can actually increase responder safety is in the area of vapor density. 'ost responders have been taught a few things about vapor density but there is much more to the topic than what is usually included in most ha%mat training sessions. As a matter of fact, vapor density is usually portrayed as a general concept but in the interest of safety a more comprehensive view is necessary. herefore, precise computations concerning the concept of vapor density will better enable response personnel to respond safely to ha%ardous materials emergencies and to conduct more effective ris( assessments. )apor density is defined as the relative weight of a gas or vapor compared to air, which has an arbitrary value of one. If a gas has a vapor density of less than one it will generally rise in air. If the vapor density is greater than one the gas will generally sin( in air. his concept is important for responders because it will indicate where the gas or vapors can generally be e*pected to be located at ha%mat releases. Accordingly, responders can better select their staging and e+uipment set$up areas as well as the ha%ard isolation %ones for the incident. Additionally, (nowledge of where the gas may be found can better define the monitoring instrument strategy at each incident. he only problem is the concept of vapor density, which has also been termed "specific gravity of vapor", offers only a vague value of where the gas or vapor may travel. In other words, response guideboo(s such as the ,epartment of ransportation -mergency !esponse .uideboo( /-!.0 which state that "vapors may be heavier than air and found in low areas" do not indicate how heavy the vapors will be. o be more precise, then, vapor densities can be calculated. Density of Air Air is a comple* mi*ture of several gases with nitrogen and o*ygen being the most prevalent. he composition of air at sea level by weight is1
2 3itrogen $ 45.567 2 &*ygen $ 86.9:7 2 &thers $ 9.697 /Argon, carbon dio*ide, neon, helium, methane, (rypton, nitrous o*ide, hydrogen, *enon, o%one0

Air, by volume, is composed of the following gases1

2 3itrogen $ 4;.<<7 2 &*ygen $ 8<.=57

2 Argon $ .=67 2 >&8 $ .<667 2 &thers $ ? .<<67

Additionally, air has a molecular weight of 8= atomic mass units /amu@s0 at sea level. In essence, this is the weight of a sample of air and which can be used for comparison purposes with other gases and vapors. Density of Gases .iven a material@s identity its molecular weight can be calculated by its chemical formula and in conjunction with a periodic table of elements. All atoms have mass and weight is the attraction of mass by gravity. For our purposes we refer to the mass of a compound as it@s weight. Finding the chemical formula for a compound and adding the weight of all of its atoms can calculate molecular weight. For instance the molecular weight of anhydrous ammonia is 94 because the formula is 3H6 where one atom of nitrogen /30 is 9A amu@s and three atoms of hydrogen /H0 is 6 amu@s. Co puting Vapor Density

o compute a compound@s vapor density simply divide the molecular weight of the compound by the molecular weight of air. his will provide a numerical value that can be compared to air@s value of one. For e*ample, Hydrogen@s molecular weight is 8 amu@s /hydrogen gas is diatomic0 and the molecular weight of air is 8= /8;.= to be e*act0. he +uotient of 8B8= e+uals .<:;. "ince this answer is below the value of one, hydrogen will rise in air /remember the HindenburgC0. >onversely, a product such as he*ane will emit vapors that will sin( in air. he computation of he*ane@s weight is based on its chemical formula of >:H9A which provides a molecular weight of ;A amu@s. he +uotient of ;AB8= is 8.=. He*ane vapors, then, are 8.= times heavier than air. Vapor Density !ne onics

o aid in remembering which gases are lighter than air some mnemonics or acronyms have been devised. A 3ew Dor( >ity fire officer around the turn of the century developed a well$ (nown mnemonic for vapor densities. o train his fellow firefighters he used the term "HA HA 'I>-" to remember the lighter than air gases. he letters stand for1
" $ Hydrogen A $ Ammonia " $ Helium A $ Acetylene

! $ 'ethane # $ Illuminating .ases /old term for natural gas0 C $ >arbon 'ono*ide $ $ -thylene his acronym was useful for years but today we now (now there are more than eight gases that are lighter than /or the same weight as0 air. o remember the 96 gases that are lighter than air a new acronym may be used as a mnemonic. he term "AH '-,I> A33A" identifies the lighter than air gases and they are1

Gas " $ Hydrogen " $ Helium " $ Hydrogen >yanide " $ Hydrogen Fluoride ! $ 'ethane $ $ -thylene D $ ,iborane # $ Illuminating .ases C $ >arbon 'ono*ide A $ Acetylene & $ 3eon & $ 3itrogen A $ Ammonia

!olecular For ula H8 He H>3 HF >HA >8HA E8H: >HAB>8H: >& >8H8 3e 38 3H6

A!% 8 A 8= 9< 9: 8; 84.4 94.A 8; 8: 9< 8; 94

Vapor Density .<4 .9A 9.< .6A .55 .=: .=: .: .=: .= .6A .=: .5=

Note; Illuminating gases is "natural gas" which is a mixture of approximately 90% methane and 10% ethane.

If you can remember this mnemonic for the lighter than air gases everything else is heavier, including the vapors from flammable li+uids. In general terms, the heavier the vapor the lower it will accumulate when released. Precautions and Applications )apor density is merely a general concept to have an idea where vapors may be found when released. However, this physical parameter is not absolute and it can be affected by1
2 air currents$ that intermi* all gases and vapors despite different vapor densities.

2 temperature$ which can cause gases and vapors to rise or sin(. 2 pressure$ altitude can affect releases because of reduced atmospheric pressure. Also, a material that is released from its container under pressure can alter vapor density e*pectations. 2 humidity$ which can be absorbed by gases or vapors and cause them to be less buoyant. 2 dew point$ which will allow water vapor in air to rise which can affect what vapors will do. 2 aerosols$ the presence of fine droplets in the vapors can cause the cloud to be heavy. &ne other precaution with the vapor density concept is the presumption that the ratios found between a gas or vapor and air are absolute. In reality, this is hardly ever the case. )apor density values are fre+uently misinterpreted in cases where a substance is released at an ambient temperature that prevents them to e*ist as a pure gas or vapor at normal atmospheric pressures. An inaccurate conclusion may mislead responders on the actions of the released gas or vapor and could compromise responder safety.

"ince many substances /li+uids0 have boiling points well above ambient temperatures they will not evaporate or evolve into pure vapors when released. /Pure vapors being defined as 9<<7 concentration above the spill0. his point is important because vapor densities are computed by using molecular weight ratios which assumes pure vapors. A more accurate method to determine the vapor density of a substance would be to compare the mi*ture of the substance@s vapor in air with that of pure air. his ratio will provide a more accurate determination of the substances vapor density. he procedure to do so is as follows1
Step ': Co pute the appro(i ate density of the pure che ical at a specific te perature. p) F 9.6:=9 G molecular weight of substance divided by the temperature / in Fo0 H A:<

Step ): Co pute the appro(i ate density of air at a pA F 6=.5:: divided by the temperature / in Fo0 H A:<

*ient te

perature.

Step +: Co pute the relative vapor density of the che ical,air i(ture. !elative vapor density F /> G p)0 H I/9<< $ >0 G pAJ divided by 9<< G pA /> stands for the "saturated concentration" of the chemical vapor in air in percent by volume0 - 'ultiplying 9<< by the vapor pressure of a substance and dividing that product by 4:< will calculate the saturated concentration. A good e*ample of this concept is with ben%ene. Een%ene has a molecular weight, based on the formula of >:H:, of 4;.9 amu@s. he vapor density ratio becomes 8.:= when ben%ene@s molecular weight of 4;.9 is divided by the molecular weight of air /8=0. his ratio would indicate that the vapors of ben%ene would accumulate near the surface of the spill and the terrain when released. In actuality, the vapors would be only slightly heavier than air by computing with the above formulas. he vapor pressure of ben%ene is 9<< mmBHg at 4=oF so multiplying 9<< mmBHg by 9<< and dividing that product by 4:< can calculate the saturated concentration. he answer is 96.9:7 which indicates the ma*imum concentration of ben%ene vapors above a release at 4=oF. #se of these values in the e+uations above, with the assumption of an air temperature of 4=oF, provides a more accurate vapor density value of 9.88. his value means that the ben%ene$air mi*ture directly above the spill of ben%ene at 4=oF is only 9.88 times heavier than air and not the 8.4 ratio that is fre+uently reported as the vapor density for ben%ene. hese e+uations and concepts are utili%ed in vapor dispersion software applications to better predict where and how far vapor clouds will travel when released. A mi*ture with vapor density values close to those of air will +uic(ly mi* with air as it drifts away from the spill. It will not ta(e long for this mi*ture to approach the density of air and behave as a neutrally buoyant vapor$air mi*ture. 3egatively buoyant mi*tures will behave as heavier$than$air mi*tures for a large distance from a spill. Also, positively buoyant mi*tures will behave as lighter$than$air mi*tures. Precision with information such as this will aid in our ris( assessments and could alter our tactics. Kith an eye toward increased personal safety consider using these concepts and formulas at your future responses. As with all concepts and theories there are e*ceptions1 be sure to remain vigilant and be carefulL And, now you (now the rest of the storyL