CEE 680

12 October 2006

 

FIRST EXAM

 

 

Closed book, one page of notes allowed.

 

Answer all questions.  Please state any additional assumptions you made, and show all work.  You are welcome to use a graphical method of solution if it is appropriate.

 

 

   Miscellaneous Information:

                    R =  1.987 cal/mole°K = 8.314 J/mole°K

                          Absolute zero = -273.15°C

                    1 joule = 0.239 calories

                    1 parsec = 19,173,511,600,000 miles

 

 

1.                  (50%) What is the pH of a 10-3 M solution of Sodium Dihydrogen Phosphate (NaH2PO4) and 10-2.7 M Sodium Monohydrogen Phosphate (Na2HPO4)?  Calculate this for each of the three conditions below.

 

                           a. 25°C, I = 0

                           b. 100°C, I = 0

                           c. 25°C, I = 0.25

 

 

 

2.                  (40%) What is the complete composition of a 1-liter volume of water to which you have added 10-1.5 M of ammonium nitrate (NH4NO3) and 10-2.5 M of the mono-sodium salt of p-Hydroxybenzoic Acid?  Approximate values (± 0.2 log units) will suffice.

 

 

 

 


 

3.                  (10%) True/False.  Mark each one of the following statements with either a "T" or an "F".

 

a. ______ An increase in ionic strength will affect hydrogen ion activity, but not hydrogen ion concentration.

 

b. ______ Titration curves (pH vs g or f) always exhibit a local minimum slope at a pH equal to the pKa of the acid/base being titrated.

 

c. ______ Electrons do not usually exist in a free state in water.

 

d. ______ Strong acids will always cause the pH to drop below 2.

 

e. ______ Alkalinity is a measure of acid neutralizing capacity.

 

f.  ______ Sodium Acetate is an amphoteric substance.

 

g. ______ The buffer intensity of a solution of a pure acid is at its lowest at a pH near the pKa of the acid.

 

h. ______ Positive DH values indicate that the reaction is exothermic

 

i.  ______ The standard assumption used for calculating the pH of an acidic solution is that the [H+] is negligible.

 

j.  ______ For a triprotic acid, the value of ao plus a1 must always equal one.

 

 

 


Selected Acidity Constants  (Aqueous Solution, 25°C, I = 0)

   NAME

   FORMULA

 pKa

Perchloric acid

HClO4 = H+ + ClO4-

-7         STRONG

Hydrochloric acid

HCl = H+ + Cl-

-3

Sulfuric acid

H2SO4= H+ + HSO4-

-3  (&2)    ACIDS

Nitric acid

HNO3 = H+ + NO3-

-0               

Hydronium ion

H3O+ = H+ + H2O

 0               

Trichloroacetic acid

CCl3COOH = H+  + CCl3COO-

 0.70

Iodic acid

HIO3 = H+ + IO3-

 0.8

Bisulfate ion

HSO4- = H+ + SO4-2

 2

Phosphoric acid

H3PO4 = H+ + H2PO4-

 2.15 (&7.2,12.3)

o-Phthalic acid

C6H4(COOH)2 = H+  + C6H4(COOH)COO-

 2.89  (&5.51)

Citric acid

C3H5O(COOH)3= H+  + C3H5O(COOH)2COO-

 3.14 (&4.77,6.4)

Hydrofluoric acid

HF = H+  + F-

 3.2

Aspartic acid

C2H6N(COOH)2= H+  + C2H6N(COOH)COO-

 3.86  (&9.82)

m-Hydroxybenzoic acid

C6H4(OH)COOH = H+  + C6H4(OH)COO-

 4.06  (&9.92)

p-Hydroxybenzoic acid

C6H4(OH)COOH = H+  + C6H4(OH)COO-

 4.48  (&9.32)

Nitrous acid

HNO2 = H+  + NO2-

 4.5

Acetic acid

CH3COOH = H+  + CH3COO-

 4.75

Propionic acid

C2H5COOH = H+  + C2H5COO-

 4.87

Carbonic acid

H2CO3 = H+  + HCO3-

 6.35 (&10.33)

Hydrogen sulfide

H2S = H+  + HS-

 7.02 (&13.9)

Dihydrogen phosphate

H2PO4- = H+  + HPO4-2

 7.2

Hypochlorous acid

HOCl = H+  + OCl-

 7.5

Boric acid

B(OH)3 + H2O = H+  + B(OH)4-

 9.2 (&12.7,13.8)

Ammonium ion

NH4+ = H+  + NH3

 9.24

Hydrocyanic acid

HCN = H+  + CN-

 9.3

p-Hydroxybenzoic acid

C6H4(OH)COO-  = H+  + C6H4(O)COO-2

 9.32

Phenol

C6H5OH = H+  + C6H5O-

 9.9

m-Hydroxybenzoic acid

C6H4(OH)COO-  = H+  + C6H4(O)COO-2

 9.92

Bicarbonate ion

HCO3- = H+  + CO3-2

10.33

Monohydrogen phosphate

HPO4-2  = H+  + PO4-3

12.3

Bisulfide ion

HS-  = H+  + S-2

13.9          

Water

H2O = H+  + OH-

14.00         

Ammonia

NH3 = H+  + NH2-

23

Methane

CH4 = H+ + CH3-

34

 

Species

kcal/mole

kcal/mole

Ca+2(aq)

‑129.77

‑132.18

CaC03(s), calcite

‑288.45

‑269.78

CaO (s)

‑151.9

‑144.4

C(s), graphite

0

0

CO2(g)

‑94.05

‑94.26

CO2(aq)

‑98.69

‑92.31

CH4 (g)

‑17.889

‑12.140

H2CO3 (aq)

‑167.0

‑149.00

HCO3- (aq)

‑165.18

‑140.31

CO3-2 (aq)

‑161.63

‑126.22

CH3COO-, acetate

‑116.84

‑89.0

H+ (aq)

0

0

H2 (g)

0

0

HF (aq)

-77.23

-71.63

F- (aq)

-80.15

-67.28

Fe+2 (aq)

‑21.0

‑20.30

Fe+3 (aq)

‑11.4

‑2.52

NO3- (aq)

‑49.372

‑26.43

NH3 (g)

‑11.04

‑3.976

NH3 (aq)

‑19.32

‑6.37

NH4+ (aq)

‑31.74

‑19.00

HNO3 (aq)

‑49.372

‑26.41

O2 (aq)

‑3.9

3.93

O2 (g)

0

0

OH- (aq)

‑54.957

‑37.595

H2O (g)

‑57.7979

‑54.6357

H2O (l)

‑68.3174

‑56.690

PO4-3 (aq)

-305.30

-243.50

HPO4-2 (aq)

-308.81

-260.34

H2PO4- (aq)

-309.82

-270.17

H3PO4 (aq)

-307.90

-273.08

SO4-2

‑216.90

‑177.34

HS- (aq)

‑4.22

3.01

H2S(g)

‑4.815

‑7.892

H2S(aq)

‑9.4

‑6.54