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15. Consider the titration of a 25.00 ml sample of 0.125 M (CH3)2NH with 0.150 M

ID: 577205 • Letter: 1

Question

15. Consider the titration of a 25.00 ml sample of 0.125 M (CH3)2NH with 0.150 M HClO4. Determine each of the following. All work must be shown for credit. (a) the pH before addition of HClO4. (b) the volume of HClO4 required to reach the equivalence point. (c) the pH after addition of 5.0 ml of HClO4. (d) the pH at half the equivalence point. (e) the pH after adding 5.00 ml of HClO4 beyond the equivalence point. (f) Neatly sketch the titration curve. Clearly label both axes of the titration curve. Label the equivalence point and the half equivalence point. Identify the buffer region.

Explanation / Answer

For:

(CH3)3NH; let us assume (CH3)3NH= B for simplicity

so

(CH3)3NH+ H2O <--> (CH3)3NH2+ + OH- becomes:

B + H2O <-> HB+ + OH-

Kb = [HB+][OH-]/[B]

so....

a)

no volume of acid

B + H2O <-> HB+ + OH-

Kb = [HB+][OH-]/[B]

in equilibrium

for 1 mol of OH- we hava always 1 mol of HB+

[HB+] = [OH-] = x (the dissociation fraction of acid)

[B] = M-x = 0.07-x (Account for dissociation!)

pKb = 3.16

(10^-3.16) = x*x/(0.125-x)

solve with quadratic formula

x = [OH-] = 0.008959

pOH = -log(Oh-) = -log(0.008959) = 2.05

pH = 14-pOH = 14-2.05= 11.95

b)

Volume erquired

mmol of base = MV = 0.125*25 = 3.125 mmol

Vacid = mmol/V = 3.125/0.150 = 20.83 mL

c)

5 mL of acid:

mmol of acid added = MV = 0.15*5 = 0.75 mmol of acid

this reacts with base:

mmol of base = MV = 25*0.125 = 3.125 mmol of base

mmol of base after reaction = 3.125 -0.75 = 2.375 mmol of base

and conjugate forms:

mmol of conjugate formed = 0 + 0.53 = 0.53

this becomes a buffer, sicne there is weak base+ conjugate acid

pOH = pKb + log(BH+/B)

pOH = 3.16+ log(0.75 /2.375 )

pOH = 2.66

pH = 14-pOH = 14-2.66= 11.34

d)

in half equivalence point

mmol of base = mmol of conjguate acid

B = HB+

pOH = pKb + log(BH+/B)

pOH = pKb

pOH = 3.16

pH = 14-3.16 = 10.84

d)

V = 20.83 mL of acid

Vtotal = 25+20.83 = 45.83

this is equivalence point!

mmol of acid = mmol of base

so..

all base/acid reacts

calculate conjugate formed

mmol of conjguate formed = MV = 25*0.125 = 3.125 mmol of conjugate

recalcualte concentration of conjugate

[BH+] = mmol/Vt = 3.125 / 45.83 = 0.068186

so..

BH+ + H2O <-> H3O+ + B

so

Ka = [H3O+][B]/[BH+]

Ka = Kw/Kb = (10^-14)/(10^-6.16) = 1.445*10^-8

so

[H3O+] = x = [B]

[BH+] = M-x = 0.068186-x

substitute

Ka = [H3O+][B]/[BH+]

becomes

1.445*10^-8= x*x/(0.068186-x)

solve for x

x = 3.138*10^-5

[OH-] = x =  3.138*10^-5

pOH = -log(OH-) -log(3.138*10^-5 ) = 4.50

pH = 14-pOH = 14-4.50 = 9.5

e)

excess

[H+] = mmol/V = (5*0.125)/(25+25) = 0.0125

pH = -log(0.0125) = 1.903

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