Consider the titration of 30 mL of 0.030 M NH3 with 0.025 M HCl. Calculate the pH after the following volumes of titrant have been added: a) 0 mL; b) 10 mL; c) 20 mL; d)35 mL; e) 36 mL; f) 37 mL.

a)10.87

b)9.66

c)9.15

d)7.71

e) 5.56

f) 3.43

Explanation:

tep 1: Data given

Volume of 0.030 M NH3 solution = 30 mL = 0.030 L

Molarity of the HCl solution = 0.025 M

Step 2: Adding 0 mL of HCl

The reaction:    NH3 + H2O ⇔ NH4+ + OH-

The initial concentration:  

[NH3] = 0.030M    [NH4+] = 0M    [OH-] = OM

The concentration at the equilibrium:

[NH3] = 0.030 - XM

[NH4+] = [OH-] = XM

Kb = ([NH4+][OH-])/[NH3]

1.8*10^-5 = x² / 0.030-x

1.8*10^-5 = x² / 0.030

x = 7.35 * 10^-4 = [OH-]

pOH = -log [7.35 * 10^-4]

pOH = 3.13

pH = 14-3.13 = 10.87

Step 3: After adding 10 mL of HCl

The reaction:

NH3 + HCl ⇔ NH4+ + Cl-

NH3 + H3O+ ⇔ NH4+ + H2O

Calculate numbers of moles:

Moles of NH3 = 0.030 M * 0.030 L = 0.0009 moles

Moles HCl = 0.025 M * 0.010 L = 0.00025 moles

Moles NH4+ = 0 moles

Number of moles at the equilibrium:

Moles NH3 = 0.0009 -0.00025 =0.00065 moles

Moles HCl = 0

Moles NH4+ = 0.00025 moles

Concentration at the equilibrium:

[NH3]= 0.00065 moles / 0.040 L = 0.01625M

[NH4+] = 0.00625 M

pOH = pKb + log [NH4+]/[NH3]

pOH =  4.75 + log (0.00625/0.01625)

pOH = 4.34

pH = 9.66

Step 3: Adding 20 mL of HCl

Calculate numbers of moles:

Moles of NH3 = 0.030 M * 0.030 L = 0.0009 moles

Moles HCl = 0.025 M * 0.020 L = 0.00050 moles

Moles NH4+ = 0 moles

Number of moles at the equilibrium:

Moles NH3 = 0.0009 -0.00050 =0.00040 moles

Moles HCl = 0

Moles NH4+ = 0.00050 moles

Concentration at the equilibrium:

[NH3]= 0.00040 moles / 0.050 L = 0.008M

[NH4+] = 0.01 M

pOH = pKb + log [NH4+]/[NH3]

pOH =  4.75 + log (0.01/0.008)

pOH = 4.85

pH = 14 - 4.85 = 9.15

Step 4: Adding 35 mL of HCl

Calculate numbers of moles:

Moles of NH3 = 0.030 M * 0.030 L = 0.0009 moles

Moles HCl = 0.025 M * 0.035 L = 0.000875 moles

Moles NH4+ = 0 moles

Number of moles at the equilibrium:

Moles NH3 = 0.0009 -0.000875 =0.000025 moles

Moles HCl = 0

Moles NH4+ = 0.000875 moles

Concentration at the equilibrium:

[NH3]= 0.000025 moles / 0.065 L = 3.85*10^-4M

[NH4+] = 0.000875 M / 0.065 L = 0.0135 M

pOH = pKb + log [NH4+]/[NH3]

pOH =  4.75 + log (0.0135/3.85*10^-4)

pOH = 6.29

pH = 14 - 6.29 = 7.71

Step 5: adding 36 mL HCl

Calculate numbers of moles:

Moles of NH3 = 0.030 M * 0.030 L = 0.0009 moles

Moles HCl = 0.025 M * 0.036 L = 0.0009 moles

Moles NH4+ = 0 moles

Number of moles at the equilibrium:

Moles NH3 = 0.0009 -0.0009 =0 moles

Moles HCl = 0

Moles NH4+ = 0.0009 moles

[NH4+] = 0.0009 moles / 0.066 L = 0.0136 M

Kw = Ka * Kb

Ka = 10^-14 / 1.8*10^-5

Ka = 5.6 * 10^-10

Ka = [NH3][H3O+] / [NH4+]

Ka =5.6 * 10^-10 =  x² / 0.0136

x = 2.76 * 10^-6 = [H3O+]

pH = -log(2.76 * 10^-6)

pH = 5.56

Step 6: Adding 37 mL of HCl

Calculate numbers of moles:

Moles of NH3 = 0.030 M * 0.030 L = 0.0009 moles

Moles HCl = 0.025 M * 0.037 L = 0.000925 moles

Moles NH4+ = 0 moles

Number of moles at the equilibrium:

Moles NH3 = 0.0009 -0.000925 =0 moles

Moles HCl = 0.000025 moles

Concentration of HCl = 0.000025 moles / 0.067 L = 3.73 * 10^-4 M

pH = -log 3.73*10^-4= 3.43