chem 127 exam 2

 October 6, 2004                    

100 points with all questions being worth 12-14 points, justify your answers / show your work

 

1.(12 pts)  a. What is the pH of a 0.0023 M solution of HCl ?

            100% dissociated so [H3O+] = 0.0023 M

            pH= -log10( 0.0023) = 2.64

            (since data is 2 sig figures, we should keep two digits behind the decimal)

            rounding off to pH = 2.6 is a bit too severe

 

   b. What is the pH of a 0.0023 M solution of NaOH ?

            pOH = -log10[OH-] = 2.64

            pH = 14.00 - pOH = 11.36

            alternatively, [H3O+] = 1.00 x 10-14 / (0.0023) = 4.35 x 10-12 M

            pH= - log10(4.35 x 10-12) = 11.36

 

 c. what is the [H3O+] of a solution that has pH 4.33 ?

            [H3O+] = 10-pH = 10-4.33 = 4.7 x 10-5 M

            the pH has two significant figures (to right of decomal) so 2 digits in the result

 

   d. Acetic Acid  has Ka = 1.80 x 10-5   ; what is pKa for this acid ?

            by definition pKa= -log10(Ka) = -log( 1.80 x 10-5) = 4.74

 

 

2. (14 pts) What is the equilibrium hydronium ion concentration, [H3O+] , 

of a 0.25 M solution of benzoic acid   (just write benzoic acid as  HA or  HB)

 Ka = 6.5 x 10-5                                                                                      

hint-- write the balanced chemical reaction; write the expression for Ka; what are the initial concentrations and the changes...

            HA + H2O ---> H3O+  + A-       (A is benzoate)

            Ka = [H3O+] x [A-] / [HA]

            initially: HA = 0.25 M;  H3O+=0 M;   A-=0 M

            change   HA (-x);   H3O+= +; A- (+x)

            equil: HA (0.25-x); [H3O+]= x;  [A-]=x

            6.5 x 10-5 = (x)*(x)/(0.25-x)

            we expect x << 0.25 so this is almopst   6.5 x 10-5 = (x)*(x)/(0.25)

            or x = square root ( 6.5 x 10-5 * 0.25) = 0.040 M = [H3O+]

 

3. (12 pts)   The gas NO2 reacts to form the gas N2O4

                   first, write the balanced equation for the reaction

                   Kp for the reaction has a value of  0.15 (atm).

A gas mixture is at equilibrium;  it contains NO2 at a pressure of 0.73 atm.

                   What is the pressure of N2O4 ?

          2 NO2 (g) --> N2O4      

            Kp = P(N2O4) / P2(NO2)

            0.15 = P(N2O4) / (0.73)2

            P(N2O4) = 0.07994 = 0.080

 

 

4. (14 points) The solubility of Ag2CrO4 (silver chromate) is   1.15 x 10-4 mol/liter

          it dissolves to form silver ions, Ag+ and chromate ions CrO42-

          what is Ksp for this species?

            Ag2CrO4 --> 2 Ag+  + CrO4-2

            Ksp = [Ag+]2 [CrO42-]

            [Ag+] = 2 x 1.15 x 10-4 M

            [CrO42-] =1.15 x 10-4

            Ksp = [Ag+]2 [CrO42-] = (2.30 x10-4)2 x 1.15 x 10-4 = 6.08 x 10-12

 

5.(12 points)  Nitrous is a weak acid :   HNO2 + H2O --->  H3O+ + NO2-

a. How does HNO2 in this equation fit the Bronstead Lowry definition of an acid

          Acid is a proton donor; HNO2 gives up H+ to H2O

b. Identify the conjugate base of Nitrous Acid

          Nitrite ion, NO2-            

c. Would you expect a  solution of Sodium Nitrite to be acidic / basic/ or neutral ?  (why?)

          basic; we just decided (part b) that nitrite ion is a base

            NO2- + H2O ---> HNO2 + OH- (basic)

            sodium is a boring spectator ion here

d. In Bronstead Lowry language, what roles are H2O and H3O+ playing here?

          in equation ,H2O accepts a proton (base) to form H3O+ (acid)

 

6 . (12 points) Use the concept of le Chatlier to answer the questions below

          (justify your answers)

The reaction 2 SO2 (g) + O2 (g) ---> 2SO3 (g) is exothermic.

If we start with a mixture of SO2, SO3 and O2 at equilibrium, would we increase / decrease /( or cause no change)  the amount of O2

Note: In grading we insisited on a justification since the answer is up/down with 50% guessing outcome.

a. if we raise the temperature of the mixture

          for an exothermic reaction, K decreases with temperature

            reaction shifts to left

            more O2 is formed

 

b. if we forced  the original mixture into a smaller volume

          reaction goes from 3 gas molecules to 2 gas molecules

            reduced volume raises pressure

            shift to right (fewer molecules of gas) relieves the stress

            therefore less O2

 

c. if we injected additional SO2 gas  into the original mixture

          relieve stress by removing SO2 ; shift to right

            this uses up O2 also

            reduces O2 pressure

d. if we injected additional O2 gas into the original mixture

          similar to (c) except we expect only partial shift

            therefore much of the added O2 will remain so P(O2) will be hgiher.

 

7 . (12 points) Silver Chloride has a very low solubility in water. Silver acetate is slightly soluble in water.        Explain why Silver acetate is more soluble in 0.1 M nitric acid than in water, but is less soluble in 0.1M HCl than it is in water.

            In HNO3, the acetate ion reacts with H+, forming acetic acid

            this reduces the [acetate] ion below what would form in water only

            so more silver acetate dissolves

            at equilibrium, [Ag+] is what ever dissolves and [acetate] is much less

 

            With HCl we need to worry bout the very low solubility of AgCl

            If we had a saturated solution of silver acetate in water and added the HCl

            we'd immediately get a preciptiate of AgCl

            the H+ would tie up acetate ions, the the [Ag+] is fixed by Ksp of AgCl

            (we'd actually convert solid silver acetate to solid silver chloride)

8. (12 points) If we mix equal volumes of 0.016 M Pb(NO3)2  and  0.080 M of KI, would we get a precipitate of PbI2 to form.   For lead Iodide,  Ksp = 8.5 x 10-9

            (Justify / explain your answer)

            After mixing [Pb2+} = 0.0080 M and [I-]= 0.040

            Q = [Pb2+] [I-]2 = 0.080 x (0.040)2 = 1.25 x 10-5

            Q much greater than Ksp so a precipitate definitely forms
(had earlier said no precipitate, but that's in error)

 

(end of exam)


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