Chapter 5 - The Gaseous State

Four Online Homework Problem Sets Chapter 5.

Start this 1st week. 1) Practice & two Reviews due 1/10; Online HW5 due 1/17. 2) Homework deadlines are firm; no excuses accepted for missing deadlines. devote class time to these when we finish chapter 6.

End-of-Chapter Problems, (next page): not to be turned in. I will

Ch. 5 lecture: will cover quickly; should finish during the 2nd week. Exam #1: Covers chapters 5, 6 & Fe & Unk Metal labs; in ~ three weeks.

Chapter 5 book homework; Pages 214-222

These will not be graded. Try to finish these before I finish the chapter 5&6 lectures. 9 35 67 11 37 73 20 38 76 21 39 81 24 45 99 25 51 28 57 30 61 32 63

I. Introduction - Some Gas Properties (Kinetic Theory)

A gas is composed of small molecules that are far apart & will compress when pressure is applied (explains V - P property of a gas). Gas molecules move randomly & the average speed is related to the temperature; a gas expands when temperature increases (explains diffusion, vapor pressure, & V - T properties of a gas). There are small attractive forces between gas molecules (small - explains why a gas diffuses & fills its container; small - explains deviations).

I. Introduction - Some Gas Properties

A gas has no set volume or shape but fills the entire container (result of small attractive forces and rapid velocity of gas molecules). A gas will liquefy when temperature is lowered or when pressure is increased (function of finite attractive forces & finite volume of gas molecules). Molecular collisions only reshuffle kinetic energy; collisions are elastic (explains lack of energy loss and evaporation).

I. Introduction


Comparison of Three States. Note the degree of order of the molecules in the three states; Solid = most ordered & Gases = most random.

II. Pressure
Pressure, P, is force per unit area P = F = m x a d2 d2 If mass is in kg, acceleration (a) in meters/sec2 (m/s2), & area (d2) in meters2 (m2); then pressure is in pascals (Pa) (kg/meters-sec2) which is the SI unit of pressure. P = m x a / d2 units are: (kg) x (m/s2) / m2 = kg m s2

1.00 Pascal (Pa) = 1.00 kg m s2 130 Pa is about equal to the pressure exerted by a nickel.

II. Pressure


The Pa was named after Blaise Pascal, a French physicist; it is a rather small unit of pressure.

Pressure exerted by a nickel (radius = 1.1 cm, mass = 5.0 g) = [5.0x10-3 kg] x [9.81 m/s2] [3.14 x (0.011m)2] = 129 kg/(ms2)

P=mxa d2

P = 130 Pa for a nickel

II. Pressure
Atmospheric pressure comes from mass of N2 & O2 being pulled to earth by gravity; a 1.00 in2 column of air going through our atmosphere would weigh 14.7 pounds at sea level. There are several common units of pressure, & you need to know the following conversion factors to 3 significant figures. Unit pascal, Pa (kg/ms2) atmospheres, (atm or a) mm Hg or torr, (mm) inches of Hg, (in. Hg) pounds per sq. in., (lb/in2) Air Pressure at Sea Level = Atmospheric Press. 101,325 Pa = 101.3 kPa 1.00 a 760. mm 29.92 in 14.7 lb/in2 (know these)

1.00 atm = 101 kPa = 14.7 lb/in2 = 760. torr or mm Hg Acceleration from gravity: g = 9.81 m/s2

II. Pressure - Measure pressure with 1) a Barometer:

Normal atmospheric pressure will support a column of liquid Hg 760. mm or 29.9 inches high.

If water is used in place of Hg, the height of the water would be 33.8 feet high since H2O is 13.5 times less dense than Hg.

II. Pressure - Measure pressure with 2) a Manometer Note: Manometer A is open to air at standard pressure and Manometer B contains a gas sample. A B

II. Pressure
For a barometer or column of liquid: P=gxdxh (know) g = 9.81 m/s2 (acceleration due to gravity) d = density of liquid (kg/m3); h = height of liquid (m) What is the pressure from a 1.00 meter tube of water in kPa? d of water = 1.00 g/cm3 (Need d in kg/m3) 1.00 g cm3 1.00 kg 1000. g (100. cm)3 (1.00 m)3 = 1.00x103 kg / m3

P = g x d x h = 9.81m/s2 x 1.00x103 kg/m3 x 1.00 m = 9.81x103 kg/ms2 = 9.81 x 103 Pa = 9.81 kPa

III. Gas Laws

A. Boyles Law - In 1601 Robert Boyle noted that the volume of a fixed amount of gas at a given temperature was inversely related to the pressure. V 1/P V = k x 1/P where k is a constant; PV = k or P2V2 = P1V1 - Example: 2.3 L of gas at 3.0 atm is expanded into a 5.0 L container. What is the new P? P2 = P1V1 = (3.0atm)(2.3L) = 1.4 atm V2 5.0L
(2 SF)

III. Gas Laws

B. Charles Law - In 1787 Jacques Charles noted a relationship between the volume of a given gas and temperature (in K). - For a given amount of gas at constant pressure, following is true (only in K): V = k x T or V/T = k V2/T2 = V1/T1 Where T is in the Kelvin scale

Example: 2.1 L of a gas at 27oC is cooled to -173oC. ( K = oC + 273.15 ) What is the new volume? 27 + 273 = 300. K (T1) - 173 + 273 = 100. K (T2) V2 = V1T2 = T1 (2.1L) (100.K) 300.K = 0.70 L
(2 SF)

III. Gas Laws



B. Charles Law continued

Note the V -T relations for several gases. Extrapolation is necessary due to liquid formation. What is - 273 oC?

Robert Boyle: British; Alchemist; Boyles Law ~ 1660 Jacques Charles: French; Balloonist; Charles Law ~ 1787

Boyle

Charles

III. Gas Laws C. Combined Gas Law V T & V k = PV T 1/P so, V T/P or V = k x T/P

P2V2 = T2

P1V1 T1

a) all units must be same on both sides of the equation, b) T must be in K, c) know these laws Use this eqn when not changing amount of gas.

III. Gas Laws

Example: 1.0 L of a gas at 10. atm & 100. K is heated to 200. K at 1.0 atm. What is the new volume V2 ? P2V2 = P1V1 T2 T1 V2 = P1V1T2 T1P2

C. Combined Gas Law

Unit P V T

Initial1 10. atm 1.0 L 100. K

Final2 1.0 atm V2 200. K

V2 = 10.atm x 1.0L x 200.K 100.K x 1.0 atm V2 = 20. L 1) estimate answer, then calc. 2) check units of answer 3) check SF of answer

III. Gas Laws

-

D. Avogadros Law

In 1811 Amedeo Avogadro related the V of gas to # of gas molecules (moles of gas). He died in 1856 & did not live to see his ideas accepted. V n (moles) at constant T & P At STP [Standard Temperature and Pressure; 1.00 atm and 0.00 oC know this] 1.00 mole = 22.4 L 22.4 L is a little larger than a basketball.

III. Gas Laws

-

D. Avogadros Law

How many L would 5.6 g of He occupy at standard temperature and pressure (STP)? Note: 22.4 L = 1.00 mole gas (at STP but not at other T or P).

5.6g He x 1.00mol He x 4.00g He

22.4 L = 31 L He 1.0 mol

III. Gas Laws V V n (Avogadro) n x T / P; V

F. Ideal Gas Law

T (Charles)

1/P (Boyle)

V = k x n x T/P; PV = nRT

Let k = R

V = RnT/P or

(Ideal Gas Law)

R = 0.0821 L x atm / (K x mol) R = 8.314 J / (K x mol)

when P in atm & V in L (know) when P in Pa & V in m3

- Ideal gas law combines all three laws; generally good to ~ 10% accuracy at normal T & P. - Use ideal gas law when dealing with the amount of a gas.

III. Gas Laws

F. Ideal Gas Law Normal Problems PV = nRT = 0.84 atm

1) What is P of 0.51 mol O2 in 15 L at 303 K? P = nRT = 0.51m x 0.0821 Latm/Km x 303 K V 15 L

2) What is V of 56.0 g of CO at 760. Torr and 0 oC? PV=nRT V = nRT/P n: 56.0 g CO x 1 mol / 28.0 g CO = 2.00 mol CO T (in K): 0 + 273 = 273 K P (in atm): 760. Torr x 1 atm / 760 torr = 1.00 atm V = nRT = 2.00m x 0.0821 Latm/Km x 273K P 1.00 atm = 44.8 L

III. Gas Laws

F. Ideal Gas Law Problems

2. MW Problem: - Calc MW if 0.55 g of a gas occupies 0.20 L at 0.97 atm & 289 K. MW = g/mole = 0.55g / ? mole = 0.55g / 8.17x10-3 m = 67g/m PV = nRT n = PV RT = (0.97 a)(0.20 L) (0.0821 La/Km)(289 K) = 8.17x10-3 m

3. Density Problem: - Calculate the density in g/L of CH4(g) at 25 oC and 0.98 atm. (Pick 1.0 mole of CH4 = 16 g/mole) g / L = 16 g / ? L = 16 g / 24.9 L PV = nRT V = 24.9 L V = nRT P = = 0.64 g/L

(1.0m)(0.0821La/Km)(298K) 0.98 a

III. Gas Laws

F. Ideal Gas Law

3. Density

Can experimentally determine MW or d of gas using the Dumas Method (1826) if know volume and mass of gas: MW = g RT/PV

III. Gas Laws

4. Stoichiometry Problem: 2 NaN3(s)


F. Ideal Gas Law

Sodium Azide = NaN3

-----)

3 N2(g) + 2e- + 2 Na+

How many L of N2(g) will be produced in a car bag by the reaction of 62.5 g NaN3 at 1.0 atm and 25 oC? PV = nRT - V = nRT/P Need n T & P - T = 273 + 25 = 298 K P = 1.0 atm - n Convert 62.5 g NaN3 to moles of N2

62.5 g NaN3 1.00 mol NaN3 3 mole N2 = 1.44 m N2 65.0 g NaN3 2 mole NaN3 V = nRT = 1.44 mol x 0.0821Latm/Kmol x 298K = P 1.0 atm 35 L N2

III. Gas Laws

G. John Daltons Law

PT = P1 + P2 + P3 Total pressure = sum of partial pressures of all gases present (Daltons Law). Mole fraction (x1 ) of a gas = Pressure fraction x1 = n 1 / n T = P 1 / P T x1 = P 1 / P T P 1 = x1 * P T

Example: 1.0 L of air at 300. K & 0.99 atm contains 0.032 mol N2 & 0.008 mol O2. Calculate 1) PN2 and 2) mole fraction

of N2.
1) PN2 = nRT/V = 0.032m x 0.0821La/Km x 300K / 1.0 L = 0.79 atm 2) a) b) xN2 = molN2 / molT = xN2 = PN2 / PT 0.032 mol / (0.032m + 0.008m) = 0.80

= 0.79 atm / 0.99 atm = 0.80

III. Gas Laws

G. Daltons Law

- If collect a gas over water then: PT = Pgas + PH2O + Pcolumn H2O - Assume T = 19.5oC & Pcol = 0 Torr for following example

III. Gas Laws

G. Daltons Law Water Pressure

III. Gas Laws

G. Daltons Law

What volume of H2 is produced when 3.0 g of Zn reacts with excess HCl? It is collected over water at 296 K & 742 Torr? Note: PH2O = 21.1 mm Hg at 296 K & Pcol water = 0.0 mm for this example.

1 Zn + 2 H+ -----) 1 H2(g) + 1 Zn2+

V = nRT/P

PT = PH2 + PH2O + Pcol water 742 = PH2 + 21.1 + 0.0 PH2 = 742 21.1 = 721 Torr (x 1atm/760 Torr) = 0.949 a
3.0g Zn 1 mol Zn 65.4 g Zn 1 mol H2 1 mol Zn = 0.0459 mol H2

V = nRT/P V = [0.0459 m
x

0.0821La/Km

296K] / 0.949 a = 1.2 L H2

IV. Miscellaneous A. Molecular Speed & Kinetic Energy

- KE1 = mv2 & KE2 = 3/2RT; m = kg of gas; v = velocity in m/s; R = 8.314J/(mol x K); KE1 in J; KE2 in J/mol; KE2 = average for gas & is a function of temperature. KE1 for one particle. - Average speed (rms) = 3RT/mw mw in kg/mol, R in j/kmol

- By knowing average KE of the gas molecules can obtain the average velocity of the molecules. The average speed of H2 molecules at 25 oC is around 4300 miles/hour; much faster than the speed of bullet from a 30-06 rifle! - There is a difference between the average speed of the gas molecules and individual molecular speeds; there are faster and slower individual molecules. - P = nRT/V; pressure is not a direct function of MW

IV. Miscellaneous

B. Grahams Law

Effusion is more simple to calculate than diffusion & is the process in which a gas flows through a small hole in a container. Grahams Law of Effusion: - rx = Rate of Effusion of gas, x. r1 r2 MW2 MW1 (know) rx 1 / MWx

IV. Miscellaneous

B. Grahams Law - Problems

1) How much faster does NH3 effuse than HCl? rNH3 / rHCl = MWHCl / MWNH3 = 36 / 17 = 1.5

2) 4.83 ml of an unknown gas effuses in the same time required for 9.23 mL of Ar to effuse. What is the MW of the unknown gas? (rate = mL / time = mL if time is same for both) runk / rAr = 4.83 mL / 9.23 mL = MWAr / MWunk [0.523]2 = [ 39.94 / MWunk ]2 MWunk = 146 (g/mole)

0.523 = 39.94 / MWunk 0.2735 = 39.94 / MWunk

IV. Miscellaneous

C. Real Gases

- Real gases do not obey ideal gas law when molecules are forced close together. - Kinetic Theory presented at the beginning was for ideal gases, & for real gases the molecules: 1) have attractive forces between molecules 2) have finite molecular size - At higher pressures &/or at lower temperatures, the deviation from the ideal gas law can be large.

IV. Miscellaneous

C. 1.00 m & 273K of a Real Gas

PV = nRT = 22.4 Latm

At 273 K & 1.00 mole of gas:

IV. Miscellaneous

C. Real Gases

In 1873 Johannes van der Waals made adjustments to the ideal gas law: [P + F1] x [V F2] = nRT (pg 208 of text)

F1 = a. This compensates for intermolecular forces F2 = b. This compensates for finite molecular size These factors of a & b are tabulated for various gases; see Table 5.7, pg 208. Most gas law calculations are good to about 5 to 10 %. Error will be greater error at high P &/or low T.

IV. Miscellaneous Boyles Law Charless Law Combined Law Avogadros Law Ideal Law Daltons Law Grahams Law V V

D. Know Gas Laws & (KE = 1/2mv2)

1/P T

at constant T & n at constant P & n at constant n at constant P & T R=0.0821 La/Kmol

P2V2/T2 = P1V1/T1 V n

PV = nRT

Pt = P1 + P2 + P3 Pn r1/r2 = MW2/MW1

Significant Figure (SF) Summary



Definition: All digits known exactly plus first uncertain one. Assume last SF is in doubt by 1 unless told otherwise. Zeros: Assume zeros are significant unless they are to the left of the first non-zero digit. Rule for multiplication & division: The answer should have the same # of SF as the least accurate part. Rule for addition & subtraction: Set up the problem and cut off the answer at the first doubtful digit. Examples: 0.0010010 = 5 SF 1.00x10-4 = 3 SF 90.11 x 4.02 / 101.1 = 3.583008902 19.89290 - 19.87 = 0.02290 1.11 x 5.22 / (111.1-110.) = 5.26745 Answer = 3.58 (3 SF) Answer = 0.02 (1 SF) Answer = 5 (1 SF Why?)