Concentrations and Other Units of Measure: (Nazaroff & Alvarez-Cohen, Section 1.C.

1)

The concept of concentration exists to answer the question: How much of the stuff is there? Definition: The concentration of a substance is the amount of it per amount of the containing material (air, water, soil). It can be expressed in various units. If the containing medium is air for example: CA = mass of A / volume of air [A] = moles of A / volume of air XA = mass of A / mass of air YA = moles of A / moles of air PA = partial pressure of A / atmospheric pressure

Unit conversion: It is often necessary to switch units, for example, to pass from a chemical reaction (in which amounts are most naturally expressed in moles) to a mass budget (in which amounts are most naturally expressed in grams). Rule 1: Mass in grams = Molecular weight x Number of moles where Molecular weight = Atomic weights

Examples: H2O: MW = 2x1 + 1x16 = 2 + 16 = 18 grams per mole CO2: MW = 1x12 + 2x16 = 12 + 32 = 44 grams per mole H2SO4: MW = 2x1 + 1x32 + 4x16 = 2 + 32 + 64 = 98 grams per mole

Atomic weights most commonly used in environmental engineering:

Hydrogen Carbon Nitrogen Oxygen Phosphorus Sulfur Chlorine Calcium

H C N O P S Cl Ca

1 12 14 16 31 32 35.5 40

(14 is for radioactive form of C !)

It is helpful to memorize the preceding numbers. For other substances, see Appendix A of Nazaroff & Alvarez-Cohen (pages 601-603)

http://periodic.lanl.gov/default.htm

Rule 2: Pressure of a gas is determined from the ideal-gas law (N&A-C, page 37)

PAV = n A RT
where PA = (partial) pressure of A, in atmosphere (atm) V = volume occupied, in m3 nA = number of moles of A in that volume R = universal constant = 82.05 10-6 atm m3 / (mol K) T = absolute temperature, in degrees Kelvin (K)

Recall: Absolute temperature (K) = temperature in degrees Celsius (oC) + 273.15 When several gases occupy a common volume (mixture), the partial pressures simply add up to the total pressure:

Ptotal = PA + PB + PC + ... = (n A + nB + nC + ...)

RT V

Properties of air: Apply ideal-gas law to air: At standard pressure (P = 1 atm) and temperature (T = 20oC = 293.15 K), One mole (n = 1 mol) of air occupies a volume V equal to

V=

nRT (1 mol)(82.05 10 -6 atm m 3 /mol K )(293.15 K ) = P (1 atm)

= 0.02405 m 3 = 24.05 L (liters)

Also, Air = mixture of 79% nitrogen + 21% oxygen MWair = (0.79) MWnitrogen + (0.21) MWoxygen = (0.79)(2x14) + (0.21)(2x16) = 22.12 + 6.72 = 28.84 grams per mole Actually, the value is 28.95 g/mol because of rare gases (heavier). This leads to: 1 / (24.05 L/mol) = 0.0416 mol/L = 41.6 mol/m3 (28.95 g/mol) / (24.05 L/mol) = 1.20 g/L

Properties of water:

Similar numbers for water (a liquid) are: H2O MW = 2x1 + 1x16 = 18 18.0 g/mol Density = 997 g/L (think 1 kg per liter) Combine the above: (997 g/L) / (18.0 g/mol) = 55.4 mol/L

Summary of unit conversion

1 mole weighs MW grams and occupies V liters MW moles grams

V liters

MW/V

moles to grams: multiply by MW moles to liters: multiply by V

liters to grams: multiply by MW/V

Common abbreviations: % ppm ppb ppt percent per mil part per million part per billion part per trillion 1 part in 100 1 part in 1000 1 part in 106 1 part in 109 1 part in 1012

where the part usually stands for mole.

Example: Todays carbon dioxide concentration in the atmosphere is reported to be 385 ppm. This means that there are 385 moles of CO2 per million moles of air.

Material Balance (Nazaroff & Alvarez-Cohen, Section 1.C.2)

Step 1: Choose a control volume This is an art rather than a science Rule 1: Boundaries must be defined clearly; you need to know whether something is inside or outside. Rule 2: Budget must yield practical information. Step 2: Select the substance for which the budget is to be made Rule: Be specific (For ex. S or SO2?) Step 3: Consider all imports and exports Add sources, subtract sinks

Examples of practical control volumes:

plume section

urban airshed

stret ch o f

entire lake
river

Accumulation

= imports - exports + sources - sinks Qin

amount at (t + dt ) amount at (t ) Accumulation = duration dt V C (t + dt ) V C (t ) dC Qout = = V dt dt mass volume of carrying fluid = Cin Qin imports = inlets volume time inlets mass volume of carrying fluid = Cout Qout exports = outlets volume time outlets

sources = S (to be specified according to application) sinks = (Decay constant) (Amount present)
= KV C V dC = Cin Qin Cout Qout + S K V C dt inlets outlets

where V = volume of control volume (in L) C = concentration of substance (in g/L) Q = volumetric flux of fluid (in L/s) S = sum of emissions (in g/s) K = decay constant (in 1/s)

Particular cases: 1. Steady state: Concentration remaining unchanged over time

dC =0 dt

inlets

in

Qin C

outlets

out

+ S KV C = 0 C =

inlets

outlets

C Q

in

Qin + S + KV

out

2. Conservative substance: No source (S = 0) and no decay (K = 0) V dC = Cin Qin Qout C dt inlets outlets

3. Isolated system: No import and no export (all Qs = 0)

S S dC = S KVC C (t ) = + Cinitial e Kt V V dt

(if S is constant over time)

Example of Material Balance

A lake contains V = 2 x 105 m3 of water and is fed by a river discharging Qupstream = 9 x 104 m3/year. Evaporation across the surface takes away Qevaporation = 1 x 104 m3/year, so that only Qdownstream = 8 x 104 m3/year exits the lake in the downstream stretch of the river. The upstream river is polluted, with concentration C = 6.0 mg/L. Inside the lake, this pollutant decays with rate K = 0.12/year.

Take volume V of lake as the control volume. Assume steady state (= situation unchanging over time)

Budget is: Budget reduces to: Solution is:

dC = QupCup QevapCevap Qdown Cdown KVC dt 0 = Qup Cup (Qdown + KV ) C Qup Cup Qdown + KV =

(Cdown = C )

C=

(9 10 4 m 3 /yr)(6.0 mg/L) = 5.19 mg/L (8 10 4 m 3 /yr) + (0.12/yr)(2 105 m 3 )

Variation on the preceding example

Un-aided (natural) remediation

Suppose now that the source of pollution in the upstream river has been eliminated. The entering concentration in the lake has thus fallen to zero. Slowly, the concentration of the pollutant decays in the lake because of its chemical decay (K term) and flushing (Q term). The equation becomes:

dC = QupCup QevapCevap Qdown Cdown KVC dt dC Q = down + K C dt V

The solution to this equation is:

Q C (t ) = Cinitial exp down + K t = (5.19 mg/L) exp(0.52 t ) V

From this solution, we can find that: It takes 1.33 years for the concentration to drop by 50%, If the acceptable concentration is 0.10 mg/L, it takes 7.6 years.

Question: If 7.6 years is too long, what can be done?

Check time scales of the problem: Residency time = V/Q = (2 x 105 m3)/(8 x 104 m3/yr) = 2.50 years Decay time = 1/K = 1 / (0.12/yr) = 8.33 years

Conclusion: Decay is slow and flushing comparatively fast. Flushing is primarily responsible for the natural cleaning of the lake. Adding a chemical to speed up decay would only bring incremental change, while increasing the flushing rate would have greater impact.

Stoichiometry
(Nazaroff & Alvarez-Cohen, Section 3.A.1)

Stoichiometry is the application of mass balance to chemical transformation. In short, atoms are conserved, and when combinations of atoms disintegrate, new combinations form with the same atoms. No loss, no gain. Example: Oxidation of glucose C6H12O6 + (???) O2 (???) CO2 + (???) H2O
First, equilibrate the Cs and Hs before and after:

C6H12O6 + (???) O2 6 CO2 + 6 H2O

Thus, we need 6x2 + 6x1 = 18 Os on the right; already 6 on left, need 12 more:

C6H12O6 + 6 O2 6 CO2 + 6 H2O

Use of stoichiometry to make material budgets:

Take oxidation of glucose again: C6H12O6 + 6 O2 6 CO2 + 6 H2O From this, we note that it takes 6 molecules of oxygen (O2) to oxidize 1 molecule of glucose (C6H12O6) 6 moles of oxygen to oxidize 1 mole of glucose MW of oxygen = 2x16 = 32 g/mol MW of glucose = 6x12 + 12x1 + 6x16 = 72 + 12 + 96 = 180 g/mol So, it takes 6x32 = 192 grams of oxygen to oxidize 180 grams of glucose. Check values on the right: Production is 6 moles of carbon dioxide (CO2) 6x(12+32) = 6x44 = 264 grams 6 moles of water (H2O) 6x(2+16) = 6x18 = 108 grams Total on left = 264 + 108 = 372 grams while total on right is = 180 + 192 = 372 grams.

In-class problems:

Combustion of butane:

C4H10

Formation of ambient ozone (O3), by three successive reactions: NO2 splits into NO and atomic O O combines with oxygen to make ozone Ozone reacts with NO to produce O2 and NO2 Answers: C4H10 + 6.5 O2 4 CO2 + 5 H2O (208 grams of oxygen needed
to burn 58 grams of butane)

NO2 NO + O O + O2 O3 O3 + NO O2 + NO2

(46 grams of nitrogen dioxide produces 48 grams of ozone)

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