Review

CHEM 162-2012 EXAM I REVIEW from 2011 exam I Dr.
Ed Tavss Review dates: 2/3 and 2/7
Chem 162-2012 Exam I review
gsolute + gsolvent = gsolution
FORMULAS mLsolute + mLsolvent mLsolution
Mass percent = grams of solute/100 g solution Mole percent = moles of solute/100 moles solution Molarity = moles of solute/L of solution
ET: Molarity is temperature dependent, but molality is not.
Difficult but important
interconversion
Molality = moles of solute/kilogram of solvent PPM = grams of solute/1,000,000 grams solution Volume percent = volume of solute/100 mL of solution Proof = 2 x Vol. %; e.g., 2 x 40 mL/100 mL solution = 80 proof Mole fraction: XA = nA/(nA + nB) XA + XB = 1
vant Hoff factor, i; i = moles of particles in solution/moles of solute dissolved Particle fraction: iXA = inA/(inA + inB)
i XA
+ iXB = 1
Raoults law: Dont use: Psoln = XsolventPosolvent Use: Psoln = iXsolventPosolvent For two volatile components: Psoln = iXsolventAPosolventA + iXsolventBPosolventB iXsolvent = insolvent/(insolvent + insolute) iXA + iXB = 1 Boiling-point elevation: T = Tf - Ti = Kbimsolute Osmotic pressure: V = inRT*
* Begin problem with this formula, not the equivalent = iMsoluteRT Note that H&P uses: T = Tf(solution) Tf(solvent) = Kbimsolute; my formula and H&Ps formula are identical. Note that H&P uses: T = Tf(solution) Tf(solvent) = -Kfimsolute; my formula and H&Ps formula are identical.
Freezing-point depression: T = Tf - Ti = -Kfimsolute
Hsoln = Hsolute-solutebondbreaking + Hsolvent-solventbondbreaking + Hsolute-solventbondforming Henrys Law: SA=kPA; MA = Solubility of dissolved gas in solution
Chem 162-2012 Exam I review S may be any unit of concentration (depending on the units of k), e.g., X, M, %.
ET note: Not everything goes through moles, e.g., volume to grams, grams to volume, atoms to molecules, molecules to atoms.
TYPES OF SOLUTIONS
solute sugar solvent A solution is a homogeneous mixture of two or more substances. The solvent is the solution component that determines the state of matter of the solution; it is usually the component present in the greatest amount. The substance(s) dissolved in the solvent is the solute(s). gsolute + gsolvent = gsolution gsolute = gsolution gsolvent gsolvent = gsolution gsolute mlsolute + mlsolvent mlsolution
SOLUTION CONCENTRATIONS CALCULATIONS

ET: Review solute, solvent, solution and their interrelationships Review D=1.00g/cm3 = 1.00 g/cc = 1.00 g/ml = 1.00g/0.001 L
Z&Z 25 (mod). A solution is made by dissolving 25 g of NaCl in enough water to make 1.00 L of solution. Assume that the density of the solution is 1.00 g/cm3. Calculate the molality. Begin with: 25g NaCl/1.00L soln End with: molality = mole of solute/kg solvent 25g NaCl/1.00 L soln mol NaCl/kg solvent Numerator: 25gNaCl/58.44gmol-1 = 0.4278 mol NaCl Denominator plan: Lsoln mLsoln gsoln kgsoln kgsolv Denominator: 1.00Lsoln x (1000mL/L) x (1g/mL) x (1kg/1000g) = l kg soln gsolute + gsolvent = gsolution kgsolute + kgsolvent = kgsolution kgsolvent = kgsolution kgsolute 1 kg solution 0.025kg solute = 0.975 kg solvent Numerator/Denominator: 0.4278molNaCl/0.975kgsolvent = 0.4388 molNaCl/kgsolvent = 0.439m
ENERGETICS OF SOLUTIONS AND SOLUBILITIES QUANTITATIVE EXPLANATION
Electrostatic interaction (ions) (= charge-charge interaction = ionic interaction) Coulombs Law: F = k(Q1 x Q2)/r2 Ion-dipole interaction Hydrogen bonding Y = N, O or F YH
Relative Strength 1000 (strong)
Relatively strong bonds
100-500(?) 30 (moderate) Y 10 (moderate) 1* (weak)
Dipole-dipole interaction (polar molec. & polar molec.) London forces (with all molecules) (non-polar molecules & non-polar molec.)
Relatively weak bonds
ENERGETICS OF SOLUTIONS AND SOLUBILITIES

QUANTITATIVE EXPLANATION
ET: Discuss G = H - TS; both enthalpy and entropy are important, but enthalpy is usually more important. Entropy can be defined as freedom [or dispersal or spread out] from confinement, or dispersal or spread out of energy. Quantitatively: Hsoln = Hsolute-solutebondbreaking + Hsolvent-solventbondbreaking + Hsolute-solventbondforming If Hsoln is zero, negative or slightly positive, the substances will dissolve. If Hsoln is moderately or strongly positive, the substances will not dissolve.
ET: Do example with CH3OH in water; pentane in water
2-8
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Energetics of solutions and solubility concepts
When an ionic salt dissolves in water, the strongest solute-solvent interaction is A. hydrogen bonding. B. London forces. C. ion-dipole. D. ion-ion forces. E. dipole-dipole. Clarification regarding water. Water is a dipole. So when water reacts with another dipole it is a dipole-dipole interaction. When the H atom in water bonds to a F, O or N atom of another molecule, this is a particularly strong dipole-dipole interaction, and is given the special name of hydrogen bonding. When an ionic salt, e.g., NaCl dissolves in water, the strongest solute-solvent bond is between these ions and water. The Na+ H2O bond is an ion-dipole bond; the Cl- H2O bond is an ion-dipole bond. An ion-dipole bond is stronger than hydrogen bonding. This question might have been written better if it said, When an ionic salt dissolves in water, the solute-solvent interaction is.
1-4
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Energetics of solutions and solubility concepts
Which of the following would result in an ideal solution? A. The enthalpy of solvation is greater in magnitude than the sum of the enthalpies of expansion of the solute and of the solvent. B. The enthalpy of solvation is equal in magnitude to the sum of the enthalpies of expansion of the solute and of the solvent. C. The enthalpy of solvation is less in magnitude than the sum of the enthalpies of expansion of the solute and of the solvent. D. The enthalpy of expansion of the solute is large. E. The enthalpy of expansion of the solute is small. Comment: Terminology to characterize solute-solute bond breakage or solventsolvent bond breakage is breakage, separation and expansion. Since expansion is neither used by this professor nor the H&P textbook, I think that its usage in this exam problem was not the best choice. An ideal solution is one in which the sum of all three enthalpies (solute-solute bond breaking, solvent-solvent bond breaking, solute-solvent bond formation) equals zero. Another way of saying this is that an ideal solution is one in which the enthalpy of the solute-solvent bond formation can be calculated from the solute-solute bond breakage and the solvent-solvent bond breakage. Examples of ideal solutions are pentane-hexane, and benzene-toluene. A. False. solution. B. True C. False. solution. D. False. E. False. This is not an ideal solution. It is a positive deviation from an ideal This is not an ideal solution. It is a negative deviation from an ideal This doesnt determine an ideal solution. Same answer as D.
HENRYS LAW GAS SOLUBILITY VS. PRESSURE

ET: The concentration of the substance in the gas phase to the concentration of the substance in the liquid phase is a constant (an equilibrium constant), which means that if you increase the pressure of a substance in the gas phase then the concentration of that substance will increase in the liquid phase, and correspondingly, if you increase the concentration of the substance in the liquid phase then the concentration (i.e., the pressure) will increase in the gas phase; identical to Raoults law except that in Raoults law the substance in its standard state is a liquid, whereas in Henrys law the substance in its standard state is a gas.
Conc. of gas in liquid phase/Conc. of gas in gas phase = constant S/P = k S=M M/P = k M = kP
6-16
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Vapor pressure of solutions calculations (Henrys Law, Raoults Law)
The concentration of helium in water is found to be 1.8310-6g/L. If the partial pressure of He is 1.210-3atm, what is the Henrys law constant kH for helium? A. 3.810-4 M/atm B. 1.510-3M/atm C. 1.8109M/atm D. 4.610-3M/atm E. 2.510-6M/atm Henrys Law: SA=kPA; or MA=kPA The unit for Henrys law constant given in the answer options is M. Hence, change the concentration of Helium in water into molarity. 1.83 x 10-6g/L x (1mol/4.00g) = 4.575 x 10-7mol/L = 4.575 x 10-7 M Now solve for k. 4.575x10-7M = k x (1.2x10-3atm) k = 3.81 x 10-4 M/atm
ET note: M = mol/L = (g/MW)/L
10
COLLIGATIVE PROPERTIES e.g., VAPOR PRESSURE LOWERING Most solution properties depend on the identity of the solute; e.g., solubility: KNO3 is more soluble in H2O than AlPO4. Colligative properties dont depend on the identity of the solute, only on the concentration (of particles) of the solute; e.g., 0.1m glucose and 0.1m urea (and 0.05m NaCl*) have the same number of particles, and therefore the same vapor pressure lowering, boiling point elevation, freezing point depression and osmotic pressure.
*Note that 1 mole of glucose provides 1 mole of particles; 1 mole of urea provides 1 mole of particles; 1 mole of NaCl provides 2 moles of particles (0.5 mole NaCl provides 1 mole of particles). ET: Discuss vapor pressure
H2 O H O H2 O 2
H2 O
C6H12 O6
C6H12O6
+ H2O Na
Cl-
Two possible mechanisms to explain vapor pressure lowering: (1) The concentration of volatile molecules in the solution has decreased, resulting in fewer molecules going into the vapor phase; (2) the entropy of the solution has increased with the addition of solute molecules; the entropy of the molecules in the gas phase is already high; therefore, adding a solute to the solvent results in a decrease in S in going from the solution to the gas phase, and a corresponding decrease in drive to put molecules into the gas phase.
11
4-2
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Vapor pressure of solutions calculations
The vapor pressure of pure benzene (C6H6) and toluene (C7H8) at 25C are 95.1 and 28.4 Torr, respectively. A solution is prepared with a mole fraction of toluene of 0.750. Determine the mole fraction of toluene in the gas phase. Assume the solution to be ideal. A) 0.750 B) 0.250 C) 0.213 D) 0.473 E)0.0280 Psoln=iXsolventAPosolventA+iXsolventBPosolventB Xbenzene=10.750=0.250 Xtoluene=0.750 Pobenzene=95.1Torr Potoluene=28.4Torr i=1forbenzeneandtoluene Pbsoln=(0.250x95.1)=23.78mm Ptsoln=(0.750x28.4)=21.30mm Themolesaredirectlyrelatedtothevaporpressure,accordingto DaltonsLaw.Therefore: Xtolueneinvapor=21.30/(21.30+23.78)=0.472
12
3-3
SKIP? Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Vapor pressure of solutions concepts (Henrys Law, Raoults Law)
Which one of the following statements is true? X. A negative deviation from Raoults law means that the observed pressure will be lower than that predicted by Raoults law. Y. Negative deviations from Raoults law are expected when Hsoln is positive (endothermic). Z. Strong interactions between solute and solvent result in negative deviations from Raoults law. A. X only B. X and Y only C. X and Z only D. Y and Z only E. Z only X. True: An example of a negative deviation from Raoults law would be a mixture of acetone and chloroform. An acetone-acetone mixture is held together by dipole-dipole interaction. A chloroformchloroform mixture is held together by dipole-dipole interaction. An acetone-chloroform mixture is held together by hydrogen bonding, stronger interaction than dipole-dipole interaction. This stronger interaction results in lower vapor pressure than predicted by Raoults law. Y. False: The stronger bonding results in an exothermic reaction; hence, a negative Hsoln. Z. True: See X above.
13
5-9
SKIP? Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Vapor pressure of solutions calculations
The mass of naphthalene (C10H8) that must be dissolved in 175 g of heptane (C7H16 ) to lower its vapor pressure by 25.0% is A. 701 g B. 525 g C. 175 g D. 74.6 g E. 101 g Let y = vapor pressure of pure heptane. Since the vapor pressure was lowered by 25.0%, then the vapor pressure of heptane in solution is 0.75y Psoln = iXsolventPosolvent Xh = nh/(nh + nn) = (gh/MWh)/((gh/MWh) + (gn/MWn)) MWheptane = 84.07 + 16.16 = 100.23gmol-1 MWnaphthalene = 120.10 + 8.08 = 128.18gmol-1 Xh = (175g/100.23gmol-1)/((175g/100.23gmol-1) + (g/128.18gmol-1)) Psoln = iXsolventPosolvent 0.75y = (((175/100.23)/((175/100.23) + (g/128.18))) x 1.00y) The ys cancel out. g = 74.6g naphthalene
14
COLLIGATIVE PROPERTY BOILING POINT ELEVATION

Boiling-point elevation: T = Tf - Ti = Kbimsolute
1 ATM.
LIQUID H2O AND GAS H2O AT EQUILIBRIUM AT 100oC (BOILING)
SALT ADDED TO H2O AT 100oC (NOTE FEWER MOLECULES OF H2O GOING INTO VAPOR)
< 1 ATM.
SALT SOLUTION AT 100 C AT EQUILIBRIUM (NOT BOILING)
15
What needs to be done for the solution to boil? Answer: Raise the temperature; hence, boiling point elevation.
9-5
SKIP? Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Colligative properties (boiling point, freezing point, osmotic pressure changes) calculations
A 2.00-g sample of an unknown nonelectrolyte is dissolved in 15.0 g of CCl4. The boiling point of the solution is 77.85 C. The boiling point constant for CCl4 is 5.03 K/m and the boiling point of pure CCl4 is 76.50 C. The molar mass of the unknown is A. B. C. D. E. 37,300 g/mol 154 g/mol 24,900 g/mol 249 g/mol 497 g/mol
Boiling-point elevation: T = Tf - Ti = Kbimsolute Tf - Ti = Kbimsolute Tf - Ti = Kbi(molesolute/kgsolvent) Tf - Ti = Kbi((masssolute/MWsolute)/kgsolvent) (77.85oC 76.50oC) = (5.03K/m) x 1 x ((2.00g/X)/0.015kg) X = 496.8g/mol
16
Freezing-point depression: T = Tf - Ti = -Kfimsolute
COLLIGATIVE PROPERTY FREEZING POINT DEPRESSION

Freezing point depression and boiling point elevation have practical applications, such as in the action of antifreeze in an automotive cooling system. Water, alone, would boil over at 100oC, and be lost through an escape valve. This would allow less water to cool the engine. Water, alone, would freeze at 0oC, and crack the engine block.
LIQUID AND SOLID WATER AT EQUILIBRIUM AT 0oC (FREEZING POINT)

Two possible mechanisms to explain freezing point depression: (1) The concentration of molecules in the solution has decreased, resulting in fewer molecules going into the solid; (2) the entropy of the solution has increased with the addition of solute molecules; therefore the molecules go from the solid to the solution to increase the entropy of the system.
SALT ADDED TO H2O (NOTE FEWER MOLECULES OF H2O GOING INTO SOLID PHASE)
SALT SOLUTION AT 0oC AT EQUILIBRIUM (NOT FREEZING)

What needs to be done to get a solid? Answer: Lower the temperature; hence, freezing point depression. Chem 162-2012 Exam I review 17
10-11
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Colligative properties (boiling point, freezing point, osmotic pressure changes) calculations
What mass of glucose (C6H12O6) in grams, must be added to 125 g H2O to lower the freezing point to 2.45C? (Kf = 1.86C m1) A. 180 g B. 23.7 g C. 237 g D. 29.7 g E.1.32g Freezing-point depression: T = Tf - Ti = -Kfimsolute Tf - Ti = -Kfi(molesolute/kgsolvent) Tf - Ti = -Kbi((masssolute/MWsolute)/kgsolvent) MW C6H12O6 = 156.18 (2.45oC0oC)=(1.86oC/m1)x1x((Xg/180.18gmol1)/0.125kg) X=29.7g
18
8-14
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Colligative properties (boiling point, freezing point, osmotic pressure changes) concepts
Which of the following aqueous solutions has the lowest freezing point? A. B. C. D. E. 0.1m glucose 0.1m NaCl 0.1m Na2SO4 0.1m NaHSO4 0.1m CH3COOH
Freezing-point depression: T = Tf - Ti = -Kfimsolute SinceKisaconstant,andmisaconstant,theonewiththelowest freezingpointistheonewiththelargestivalue.

A.GlucoseGlucoseOrganicmolecules,otherthanorganicacids,dontdissociate.i=1 B.NaClNa++Cli=2
C.Na2SO42Na++SO42i=3
D.NaHSO4Na++HSO4HSO4isaveryweakacid,anddissociatesvery slightlyi=2(perhaps2.01?2.02?) E.CH3COOHCH3COO+H+Organicacidsdissociateveryweakly.i1.01
19
COLLIGATIVE PROPERTY OSMOTIC PRESSURE

ET: Semipermeable membranes: Some substances go through the membrane; other substances are too Osmotic pressure formula: V = nRT; = (n/V)RT; = MRT large to go through.
LIQUID WATER AND LIQUID WATER, AT EQUILIBRIUM
When a solution is on one side of a semipermeable membrane and the pure solvent on the other side, the solvent tends to move across the membrane. This is osmosis. Note that the solute molecules are too large to fit through the pores of the membrane.
STARCH ADDED TO WATER (NOTE FEWER MOLECULES OF H2O LEAVING MEMBRANE)
ET: The osmotic pressure is the pressure resulting from the push up the tube.
Chem 162-2012 Exam I review STARCH
SOLUTION AT EQUILIBRIUM
20
11-25
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Colligative properties (boiling point, freezing point, osmotic pressure changes) calculations
The mass of glucose (MW = 180.2) required to prepare 2.00 L of solution with an osmotic pressure of 1.50 atm at 25 C is A. 263 g B. 1.46 g C. 22.1 g D. 44.6 g E. 132 g Osmotic pressure: V = inRT V = i(g/MW)RT 1.50 atm x 2.00L = 1 x (g/180.2gmol-1) x 0.08206Latmdeg-1mol-1 x 298K X = 22.1g
21
COLLOIDS
A colloid is a dispersion in which the dispersed matter has one or more dimensions (length, width, or thickness) in the range from about 1nm to 1000 nm. The particles dont settle out (suspension) but they arent dissolved into individual molecules either (solution). Particle Precipitation Size No <1nm No 1nm to 1000 nm Fluid appearance Clear Usually cloudy Tyndall Effect** No Yes
Solution Colloid*
Example NaCl in H2O Starch in H2O, milk, gelatin, fog, steam, hair spray
Phase Homogen Varies
Suspension Sand in H2O
Heterogen
Yes
>1000 nm
Cloudy
Yes
*Also called colloidal suspension or colloidal dispersion. **The Tyndall effect is the scattering of light by colloidal particles, which makes a colloidal dispersion distinguishable from a true solution. Colloids occur in any phase. Gas phase: aerosol Liquid phase: emulsion Solid phase: sol
ET: A colloid is usually a cloudy dispersion.
22
12-15
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 12 Properties of Solutions Miscellaneous
Which one of the following is an example of a colloidal suspension? A. mayonnaise B. steel C. filtered sea water D. sand E. diamond Note: I think the word suspension is confusing, since mayonnaise is a dispersion, and not a suspension. However, the term colloidal suspension is frequently used to distinguish a colloid from a typical suspension. A typical suspension would be a mixture of sand and water immediately after shaking. A. B. C. D. E. Mayonnaise is a colloidal dispersion (aka colloidal suspension). Steel is a solid solution. Filtered sea water is a solution. Sand is a mixture. Diamond is an allotropic form of an element.
23
CHAPTER 14 FORMULAS
ET: Rate = speed. Using a diagram with Y being 100 lbs and 110 lbs, and days 0 to 5, show that the increase in weight = slope = (Y2 Y1)/(X2 X1) = +2lb/day. Decrease in weight = -increase in weight = -slope = -(Y2 Y1)/(X2 X1) = -2lb/day. ET: Point out that table in middle of page contains the key formulas in kinetics. Discuss these formulas at beginning of recitation, focusing on 1o reaction.
C12H22O11(sucrose) + H2O 2 C6H12O6(glucose) Rate of sucrose disappearance = -( [sucrose])/( time) = -([sucrosef] - [sucrosei])/(tf - ti) Rate of glucose appearance = 2 x Rate of sucrose disappearance aA + bB cC + dD Rate of reaction = -(1/a)([A]/t) = -(1/b)([B]/t) = (1/c)([C]/t) = (1/d)([D]/t) Rate of a reaction may be written several ways. Reaction: 2A + 3B + C 2D Rate of disappearance of A = k[A]m[B]n[C]p Rate = k[A]m[B]n[C]p A/t = k[A]m[B]n[C]p d[A]/dt = k[A]m[B]n[C]p Integrated Reaction Differentiated rate law Order Reaction Rate** RATE LAW*** (y = mx + b) 0 AvgRate = -(C2-C1)/(t2-t1) Rate = k[C]o =k [C]t = -kt + [C]o 1 AvgRate = -(C2-C1)/(t2-t1) Rate = k[C]1 2 AvgRate = -(C2-C1)/(t2-t1) Rate = k[C]2 ln[C]t = -kt + ln[C]o 1/[C]t = kt + 1/[C]o Half-life* t1/2 = [C]o/2k t1/2 = 0.693/k k units M1s-1 Mos-1
** Rate of appearance = +slope; rate of disappearance = -rate of appearance = -slope. *** Differentiated Rate Law may be for more than one component, e.g., Rate = k[C]1[D]2
t1/2 = 1/(k[C]o) M-1s-1
*Half-lives: For a zero order reaction, each successive half-life is the time of the preceding one. For a first order reaction, each successive half-life is equal in time to the preceding one. For a second order reaction, each successive half-life is double time of the preceding one. Arrhenius equation: k = Ae(-Ea/RT) ln k = -Ea/RT + ln A A = frequency factor = combination of steric factor and collisional frequency Ea = energy of activation ln k2 - ln k1 = (-Ea/RT2) - (-Ea/RT1) ln (k2/k1) = -(Ea/R)[(1/T2) - (1/T1)]
24
Reaction Rate
4PH3(g) P4(g) + 6H2(g) The rate of disappearance of PH3 = negative slope of the line = -(Y2 Y1)/( X2 X1) = -((0 0.0096)/(4-0)) = 0.0024 M/s Note that the rate of appearance of H2 = 0.0036M/s = 3/2 the rate of disappearance of PH3, 0.0024M/s. Note that the rate of appearance of P4 = 0.0006M/s = 1/4 the rate of disappearance of PH3, 0.0024M/s.
0.0144
(X2,Y2
0.0144M
CONCENTRATION (M)
0.0120 0.0096 0.0072 0.0048 0.0024 x1,y1
H2 PH3
(X2,Y
P4
0 (X1,Y1
0.0024M x2,y2
TIME (s)
25
15-23
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates, rate constants, reaction orders, half-lives concepts
Consider the reaction 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g). If the rate of disappearance of O2 is 0.145 atm/s, what is the rate of appearance of H2O? A. 0.145 atm/s B. 0.121 atm/s C. 0.0290 atm/s D. 0.870 atm/s E. 0.174 atm/s The rate of appearance of H2O is 6/5th the rate of disappearance of O2 . (6/5) x 0.145 atm/s = 0.174 atm/s
26
Hypothetically: Reaction is 2nd order with respect to C12H22O11 and zero order with
ET: Discuss formation of plot from data; then discuss definitions
C12H22O11 + H2O 2C6H12O6 (hypothetical example) C (M) Rate Plot

1
X1,Y1
0.9
0.8
X2,Y2
Rate = -(Y2 - Y1)/(X2 - X1) Note 1,2,3,4 Rate = -(0.8-1.0)/(0.25-0) = +0.80M/s Note2 Rate = k[C12H22O11]m[H2O]n Note 5,7 Given: m = 2; n = 0 Rate=k[C12H22O11]2[H2O]0=k[C12H22O11]2 0.80M/s = k x [0.9]2 k = 1.0 Note 6
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 Rate = k[C]2 k=1
Time (s) 0 0.1 0.3 0.4 0.7 1.0 1.5 2.3 4.0
SUCROSE CONCENTRATION (M)
0.7
0.6
Note1 Rate: Change in concentration of a reactant or product per change in time. 2 Average rate: Rate calculated between two points. 3 Instantaneous rate: Rate calculated at one point. 4 Initial rate: Instantaneous rate at time close to zero 5 Rate law: Relationship between rate of reaction and concentration of reactants ET: Discuss rate laws 6 Rate constant: The proportionality value k in a rate law; it is a constant constant 7 Order of reaction: The exponent in the rate equation; shows the relationship between the rate of a reaction and the reactant concentration. A zero order reaction is not controlled by the concentration of the reactant. A zero order reaction might be controlled by things not in the stoichiometric equation, such as light or a catalyst. The order cannot be determined from the stoichiometric equation; it must be determined experimentally. The order is the sum of the exponents in the rate equation, so Rate = k[A]2[B]3 is a fifth order reaction.
ET: Focus on best insstananeous rate.
0.5
X1,Y1
0.4
Rate = -(Y2 - Y1)/(X2 - X1) Rate = -(0.3- 0.5)/(2.33-1.0) = +0.15M/s Rate = k[C12H22O11]m[H2O]n Given: m = 2; n = 0 Rate=k[C12H22O11]2[H2O]0=k[C12H22O11]2 0.15M/s = k x [0.4]2 k = 1.0
X2,Y2
0.3
0.2 0 1 2 3 4 5
27
TIME (s)
PRIORITIES IN SOLVING KINETICS PROBLEMS

FIND REACTION ORDER Use method of initial rates - If initial rates are available*
*If initial rates are not available they can be calculated, but that is probably not worth the time on an exam.
Evaluation of half-life data Identifying integrated rate law straight line graph - From actual graph - From description of graph Recognizing k units Plugging numbers into equations to get a constant k. (the constant-constant method) - Differentiated rate law equation - Integrated rate law equation - Half-life equation FIND THE RATE CONSTANT After identifying reaction order, plug numbers into - Differentiated rate law equation or - Integrated rate law equation or - Half-life equation Slope or negative slope of integrated rate law graph Note: Diff. rate law equation contains conc. and rate terms. Integ. rate law and t1/2 equations contain conc. and time terms. ONCE REACTION ORDER AND RATE CONSTANT ARE KNOWN Use table of formulas for everything else.
Chem 161-2012 Exam I review 28
INITIAL RATES METHOD FOR DETERMINATION OR REACTION ORDER

16-6 Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates,rate constants, reaction orders, half-lives calculations
Initial rate data were obtained for the following reaction: 2A(g) + 3 B(g) C(g) + D(g) Experiment 1 2 3 Initial [A] Initial [B] Initial Rate mol/L mol/L 0.15 0.30 0.15 0.10 0.10 0.20 4.510-1 1.8 9.010-1
What is the rate law for the reaction?
A. rate = k [A] [B]

2
B. C. D. E.
rate = k [A] rate = k [A][B] rate = k [A]2[B]3 rate = k [A][B]2 Initial [A] Initial [B] Initial Rate mol/L mol/L 0.15 0.30 0.15 0.10 0.10 0.20 0.45 1.8 0.90
Experiment 1 2 3
Solvethisbytheinitialratemethod. Rate=k[A]m[B]n Exp.2:1.8=k[0.30]m[0.10]n Exp.1:0.45=k[0.15]m[0.10]n 4=2m m=2 Exp.3:0.90=k[0.15]m[0.20]n Exp.1:0.45=k[0.15]m[0.10]n 2=2n n=1 Rate=k[A]2[B]1=k[A]2[B]
29
Determining the Reaction Order by Graphing

PLOTTED FOR ZERO ORDER REACTION
1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 1000 2000 3000 4000
Time PLOTTED FOR FIRST ORDER REACTION
Time (s) 0 120 1 300 1 600 1 1200 1 1800 1 2400 1 3000 1 3600 1
[H2O2](M) 1.00 0.91 0.78 0.59 0.37 0.22 0.13 0.082 0.050
[H2O2]
ln [H2O2]
-0.5 0 -1 -1.5 -2 -2.5 -3 -3.5
1000
2000
3000
4000
Based on graph, rate = k[H2O2]1
Time
PLOTTED FOR SECOND ORDER REACTION

25 20
1/[H2O2]
15 10 5 0 0 1000 2000 3000 4000
Time
30
13-17
SKIP? Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates, rate constants, reaction orders, half-lives concepts
A graph of 1/[A] vs. time gives a straight line. Which rate law is consistent with this graph? A. r = k[A]2 B. r = k C. r = k[A] D. r = k[A]-1 E. r = k[A]3 The integrated rate law for a second order reaction is 1/[C]t = kt + 1/[C]o. Hence, a plot of (1/[C]t) in the y axis, vs. t on the x axis, gives a straight line for a second order reaction. A is the only option for a second order reaction.
31
DETERMINATION OF REACTION ORDER BY UNIT IDENTIFICATION
Made-up problem: What is the reaction order if the rate constant is 3.2 x 10-4M-5s-1? Reaction Order 0 1 2 3 4 5 6 7 Units of k M1s-1 = Ms-1 M0s-1 = s-1 M-1s-1 M-2s-1 M-3s-1 M-4s-1 M-5s-1 M-6s-1
32
14-22
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates, rate constants, reaction orders, half-lives concepts
Which units of k are consistent with a fifth order rate law? A. M-5 s-1 B. M-4 s-1 C. M4 s-1 D. M-4 s-4 E. M s-1 0 order: M1s-1 1st order: M0s-1 2nd order: M-1s-1 3rd order: M-2s-1 4th order: M-3s-1 5th order: M-4s-1
33
DETN. OF RATE CONSTANT USING HALF-LIFE; THEN FIND SOMETHING ELSE

17-7 Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates, rate constants, reaction orders, half-lives calculations D
A second-order reaction has a half-life of 20.0 s when the initial reactant concentration is 1.50 M. What will be the reactant concentration after 30.0 s? A. 0.273 M B. 0.514 M C. 0.429 M D. 0.600 M E. 0.333 M Find k. t1/2 = 1/(k[C]o) 20.0 s = 1/(k[1.50]) k = 0.03333 Use the integrated rate law to find [C]t. 1/[C]t = kt + 1/[C]o 1/[C]t = (0.03333 x 30.0) + 1/[1.50]o [C]t = 0.600M
ET: Point out that all four equations might be used, in tandem, to solve a problem.
34
DETN. OF RATE CONSTANT USING HALF-LIFE; THEN FIND SOMETHING ELSE

18-10 Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13A Kinetics Rates,rate constants, reaction orders, half-lives calculations D
The half life of a first order reaction is 2.64s. How long must the reaction proceed before only 1.56% of the reactant remains? A. 2.64s B. 338s C. 10.6s D. 15.8s E. 26.4s Find k. t1/2 = 0.693/k 2.64s = 0.693/k k = 0.2625s-1 Find time. ln[C]t = -kt + ln[C]o ln[0.0156]t = -(0.2625 x t) + ln[1.00]o ln[0.0156]t = -(0.2625 x t) t = 15.85 s
35
ARRHENIUS EQUATION INCLUDING ENERGY OF ACTIVATION Arrhenius equation: k = Ae(-Ea/RT) ln k = -Ea/RT + ln A k in the Arrhenius equation is the same as the k in the rate equ. Rate = k[X]m[Y]n Ea = energy of activation R = 8.314Jdeg-1mol-1 T = oK A = frequency factor = combination of collisional frequency and steric factor
36
Z&Z 74 (modif.) ln k = -Ea/RT + ln A The energy profile for a certain reaction that proceeds by a one-step mechanism is
activated complex (transition state) I CH3 Br
Activation Energy
E
Reactant(s) e.g., I- + CH3-Br
Product(s) I-CH3 + Br-
Reaction Coordinate
ET: Possible way to discuss Activation Energy is (a) with molecular models, e.g., I- + CH3Br CH3I + Br-; (b) going from one boyfriend through two boyfriends to one boyfriend, (c) going from a high-school-level job through a college education to a college-level job. ET: The more energy it takes to break the reactant bonds, the greater the activation energy.
37
24-18
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13B Kinetics Reaction mech., activation energy & catalysts calculations
The rate constant for a cis-trans isomerization of proline is 2.7 102 s1 at 25C and 6.2 102 s1 at 115 C. What is the activation energy for the reaction, in kJ/mol? A. 0.089 kJ/mol B. 87 kJ/mol C. 0.0045 kJ/mol D. 13 kJ/mol E. 8.9 kJ/mol ln (k2/k1) = -(Ea/R)[(1/T2) - (1/T1)] T1 = 298K k1 = 2.7 x 10-2 s-1 -2 -1 k2 = 6.2 x 10 s T2 = 388K ln ((6.2x10-2)/(2.7x10-2)) = -(Ea/8.314)[(1/388) - (1/298)] Ea = 8.88 x 103 J/mol = 8.9 kJ/mol Note: Most energies of activation are approximately 30 150 kJ/mol. The low value of 8.9 kJ/mol can be explained if this reaction is an enzymatic catalysis.
38
25-24
A catalyst decreases the activation energy for a reaction by 15 kJ/mol. How much faster is the reaction at 25oC with the catalyst than without? Assume that the frequency factor, A, is constant. A. B. C. D. E. 6.00 times faster 426 times faster 613 times faster 15 times faster 15000 times faster
ln k = -Ea/RT + lnA ln k2 = -Ea2/RT2 + lnA2 ln k1 = -Ea1/RT1 + lnA1 Subtract ln k1 from lnk2. lnk2 lnk1 = -Ea2/RT2 + lnA2 (-Ea1/RT1 + lnA1) ln(k2/k1) = Ea1/RT1 + lnA1 -Ea2/RT2 + lnA2 At constant A: ln(k2/k1) = Ea1/RT2 - Ea2/RT2 k2 = faster reaction = catalyzed reaction = reaction with lower Ea ln (k2/k1) = (84000/(8.314x298)) (69000/(8.314x298)) k2/k1 = 426
39
REACTION MECHANISM FUNDAMENTALS

Elementary steps
Transition state ABA (Activated complex) Rate det step
1st step: Slow 2nd step: Rapid reversible

Molecularity: termolecular
Activation Energy
Stoichiometry of this elementary step: 2A + B A2B Rate of this elementary step: Rate = k[A]2[B]
2A + B
E or H ABA
B A A
(Reactive) interm
Product
ET: Discuss fundamentals
40
22-21
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13B Kinetics Reaction mechanisms, activation energy & catalysts concepts Consider the following energy profile for a reaction that proceeds by a two-step mechanism A B B P. Which step is the rate determining step?
A. B P
B. A B C. A P D. B A E. P B AB BP AP A. B. C. D. E. B P is the step of greatest activation energy. Hence it is the slow step. A B is the rapid reversible step just prior to the slow step. A P is not a step. It is the sum of two steps. B A is a step going in the wrong direction. P B is a step going in the wrong direction
41
CATALYSIS MECHANISM FUNDAMENTALS

A catalyst is a substance that speeds up a reaction without being consumed by it.
42
H2O2 H2O2 + I
-
OI-
*Data fictitious
H2O + O2 H2O + O2 + I-
43
20-19
Chem 162-2011 Exam I Hill & Petrucci et al. 4th edition Chapter 13B Kinetics Reaction mechanisms, activation energy & catalysts concepts
H2O2 + OI H2O+ O2 + I slow step A) H2O2 B) H2O C) I D) OI E) O2
Consider the following 2-step mechanism. Which of the species in the mechanism is the catalyst? fast step H2O2 + I H2O+ OI
A. H2O2 is a reactant, because it is present at the beginning and not at the end of the reaction. B. H2O is a product, because it is present at the end and not at the beginning of the reaction. C. I- is the catalyst. Its there at the beginning and end of the reaction. and not in the middle of the rection. D. OI- is a reactive intermediate. It is not present at the beginning or end of the reaction. It forms in a middle step, and decomposes in a middle step. E. O2 is a product, because it is present at the end and not at the beginning of the reaction.
44
21-20
Which statement is not correct regarding the function of a catalyst? A) It lowers the activation energy. B) It changes the mechanism of a reaction. C) It affects the rate of a chemical reaction. D) It is regenerated in the reaction. E) It lowers the energy of the product causing the reaction to be more exothermic. A.Correct B.Correct C.Correct D.Correct E.False.Acatalystdoesntaffecttheenergyofthereactantor product.Hence,ithasnoeffectonH.
45
20-19
H2O2 + OI H2O+ O2 + I slow step A) H2O2 B) H2O C) I D) OI E) O2
Consider the following 2-step mechanism. Which of the species in the mechanism is the catalyst? fast step H2O2 + I H2O+ OI
A. H2O2 is a reactant, because it is present at the beginning and not at the end of the reaction. B. H2O is a product, because it is present at the end and not at the beginning of the reaction. C. I- is the catalyst. Its there at the beginning and end of the reaction. and not in the middle of the rection. D. OI- is a reactive intermediate. It is not present at the beginning or end of the reaction. It forms in a middle step, and decomposes in a middle step. E. O2 is a product, because it is present at the end and not at the beginning of the reaction.
46
RATE OF A REACTION WITH A SLOW STEP FOLLOWED BY A FAST STEP OR OF A REACTION WITH ONLY ONE STEP
Rate det step
1st step: Slow 2nd step: Rapid
2A + B
2A + B A2B: Rate = k[A]2[B]
ET: Discuss fundamentals
47
RATE OF A REACTION WITH A SLOW STEP PRECEDED BY A FAST STEP
Rate det step Reactant
1st step: Rapid reversible 2nd step: Slow Total Activation Energy
E
Interm. E Product
Reaction Coordinate
48
23-1
The reaction 2A + B C has the following mechanism. A + B D fast equilibrium D + B E slow step E + A C + B fast step Which rate law is consistent with the above mechanism? A) Rate = k [A]2 [B] B) Rate = k [A][B]2 C) Rate = k [A][B] D) Rate = k [A]2 [B]2 E) Rate = k [A ]2 The rate is based on the slow step. Rate = [D][B] D is a reactive intermediate and therefore is not in the experimentally determined stoichiometric equation. Therefore, replace [D] Rate forward = Rate reverse k1 = rate forward in the fast equilibrium step k-1 = rate reverse in the fast equilibrium step Rate forward = k1 x [A][B] Rate reverse = k-1 x [D] k1[A][B] = k-1[D] [D] = (k1/k-1)[A][B] Rate = ((k1/k-1)[A][B]) x [B] = k[A][B]2
49
ENZYME CATALYSIS
Enzymes Are biological catalysts - Provide an alternate mechanism with lower activation energy than the uncatalyzed reaction Increase the rate of biochemical reactions by factors ranging from 106 to 1018 Are highly specific, acting on only certain reactant molecules (called substrates), while leaving the rest of the system unaffected. Usually homogeneous catalysis (substrate and enzyme in aqueous solution); sometimes heterogeneous Are in living organisms High molecular weight proteins Used to be considered strictly lock and key model, but now more induced fit model
Enzymes are biological catalysts. They attach to a reactant called a substrate. The enzyme-substrate combination can then break down into the desired product much faster than just the substrate itself. In the process the enzyme is regenerated. The reaction may be represented by:
E + S ES
(slow) (fast)
E = enzyme; S = substrate P = product

50
ES E + P
Total: E + S P

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CHEM 162-2012 EXAM I REVIEW from 2011 exam I Dr.

Ed Tavss Review dates: 2/3 and 2/7

Chem 162-2012 Exam I review

gsolute + gsolvent = gsolution

FORMULAS mLsolute + mLsolvent mLsolution

Difficult but important

Freezing-point depression: T = Tf - Ti = -Kfimsolute

Chem 162-2012 Exam I review

SOLUTION CONCENTRATIONS CALCULATIONS

Chem 162-2012 Exam I review

ENERGETICS OF SOLUTIONS AND SOLUBILITIES QUANTITATIVE EXPLANATION

Relative Strength 1000 (strong)

Relatively strong bonds

100-500(?) 30 (moderate) Y 10 (moderate) 1* (weak)

Relatively weak bonds

Chem 162-2012 Exam I review

ENERGETICS OF SOLUTIONS AND SOLUBILITIES

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

HENRYS LAW GAS SOLUBILITY VS. PRESSURE

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

COLLIGATIVE PROPERTY BOILING POINT ELEVATION

LIQUID H2O AND GAS H2O AT EQUILIBRIUM AT 100oC (BOILING)

Chem 162-2012 Exam I review

SALT SOLUTION AT 100 C AT EQUILIBRIUM (NOT BOILING)

Chem 162-2012 Exam I review

Freezing-point depression: T = Tf - Ti = -Kfimsolute

COLLIGATIVE PROPERTY FREEZING POINT DEPRESSION

LIQUID AND SOLID WATER AT EQUILIBRIUM AT 0oC (FREEZING POINT)

SALT SOLUTION AT 0oC AT EQUILIBRIUM (NOT FREEZING)

Chem 162-2012 Exam I review

Freezing-point depression: T = Tf - Ti = -Kfimsolute SinceKisaconstant,andmisaconstant,theonewiththelowest freezingpointistheonewiththelargestivalue.

Chem 162-2012 Exam I review

COLLIGATIVE PROPERTY OSMOTIC PRESSURE

LIQUID WATER AND LIQUID WATER, AT EQUILIBRIUM

STARCH ADDED TO WATER (NOTE FEWER MOLECULES OF H2O LEAVING MEMBRANE)

Chem 162-2012 Exam I review STARCH

Chem 162-2012 Exam I review

Phase Homogen Varies

Suspension Sand in H2O

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

t1/2 = 1/(k[C]o) M-1s-1

Chem 162-2012 Exam I review

0.0120 0.0096 0.0072 0.0048 0.0024 x1,y1

Chem 162-2012 Exam I review

Chem 162-2012 Exam I review

C12H22O11 + H2O 2C6H12O6 (hypothetical example) C (M) Rate Plot

SUCROSE CONCENTRATION (M)

Chem 162-2012 Exam I review

PRIORITIES IN SOLVING KINETICS PROBLEMS

INITIAL RATES METHOD FOR DETERMINATION OR REACTION ORDER

What is the rate law for the reaction?

A. rate = k [A] [B]

Chem 161-2012 Exam I review

Determining the Reaction Order by Graphing

Time PLOTTED FOR FIRST ORDER REACTION