Answer:
A. pH using molar concentrations = 2.56
B. pH using activities = 2.46
C. pH of mixture = 2.56
Step-by-step explanation:
A. pH using molar concentrations
ClCH₂COOH + H₂O ⇌ ClCH₂COO⁻ + H₃O⁺
HA + H₂O ⇌ A⁻ + H₃O⁺
We have a solution of 0.08 mol HA and 0.04 mol A⁻
We can use the Henderson-Hasselbalch equation to calculate the pH.
![\begin{array}{rcl}\text{pH} & = & \text{pK}_{\text{a}} + \log \left(\frac{[\text{A}^(-)]}{\text{[HA]}}\right )\\\\& = & 2.865 +\log \left((0.04)/(0.08)\right )\\\\& = & 2.865 + \log0.50 \\& = &2.865 - 0.30 \\& = & \mathbf{2.56}\\\end{array}](https://img.qammunity.org/2021/formulas/chemistry/college/uqojex3vvn5e26vd3vpi6cnp5x9ojp842w.png)
B. pH using activities
(i) Calculate [H⁺]
pH = -log[H⁺]
![\text{[H$^(+)$]} = 10^{-\text{pH}} \text{ mol/L} = 10^(-2.56)\text{ mol/L} = 2.73 * 10^(-3)\text{ mol/L}](https://img.qammunity.org/2021/formulas/chemistry/college/vnmmu3wm6rfhksyjx9h9dhhoiiy1pg40r6.png)
(ii) Calculate the ionic strength of the solution
We have a solution of 0.08 mol·L⁻¹ HA, 0.04 mol·L⁻¹ Na⁺, 0.04 mol·L⁻¹ A⁻, and 0.00273 mol·L⁻¹ H⁺.
The formula for ionic strength is
![I = (1)/(2) \sum_(i) {c_(i)z_(i)^(2)}\\\\I = (1)/(2)\left [0.04* (+1)^(2) + 0.04*(-1)^(2) + 0.00273*(+1)^(2)\right]\\\\= (1)/(2) (0.04 + 0.04 + 0.00273) = (1)/(2) * 0.08273 = 0.041](https://img.qammunity.org/2021/formulas/chemistry/college/kcr6m2fr585ogmaja37msmmybgw7zdho2n.png)
(iii) Calculate the activity coefficients
![\ln \gamma = -0.510z^(2)√(I) = -0.510(-1)^(2)√(0.041) = -0.510* 0.20 = -0.10\\\gamma = 10^(-0.10) = 0.79](https://img.qammunity.org/2021/formulas/chemistry/college/djtqazmwpo6k8eqopa64ypckscay9267ym.png)
(iv) Calculate the initial activity of A⁻
a = γc = 0.79 × 0.04= 0.032
(v) Calculate the pH
![\begin{array}{rcl}\text{pH} & = & \text{pK}_{\text{a}} + \log \left(\frac{a_{\text{A}^(-)}}{a_{\text{[HA]}}}\right )\\\\& = & 2.865 +\log \left((0.032)/(0.08)\right )\\\\& = & 2.865 + \log0.40 \\& = & 2.865 -0.40\\& = & \mathbf{2.46}\\\end{array}\\](https://img.qammunity.org/2021/formulas/chemistry/college/f7loekrq5y5vfvdft9dypcoa7171ffjgil.png)
C. Calculate the pH of the mixture
The mixture initially contains 0.08 mol HA, 0.04 mol Na⁺, 0.04 mol A⁻, 0.05 mol HNO₃, and 0.06 mol NaOH.
The HNO₃ will react with the NaOH to form 0.05 mol Na⁺ and 0.05 mol NO₃⁻.
The excess NaOH will react with 0.01 mol HA to form 0.01 mol Na⁺ and 0.01 mol A⁻.
The final solution will contain 0.07 mol HA, 0.10 mol Na⁺, 0.05 mol A⁻, and 0.05 mol NO₃⁻.
(i) Calculate the ionic strength
![I = (1)/(2)\left [0.10* (+1)^(2) + 0.05 *(-1)^(2) + 0.05*(-1)^(2)\right]\\\\= (1)/(2) (0.10 + 0.05 + 0.05) = (1)/(2) * 0.20 = 0.10](https://img.qammunity.org/2021/formulas/chemistry/college/pmqpx57mg2bgdw7t0lu77pjokktwz3avm8.png)
(ii) Calculate the activity coefficients
![\ln \gamma = -0.510z^(2)√(I) = -0.510(-1)^(2)√(0.10) = -0.510* 0.32 = -0.16\\\gamma = 10^(-0.16) = 0.69](https://img.qammunity.org/2021/formulas/chemistry/college/t78hrjp4s4n0qciz922nwckml2t94nnbtd.png)
(iii) Calculate the initial activity of A⁻:
a = γc = 0.69 × 0.05= 0.034
(iv) Calculate the pH
![\text{pH} = 2.865 + \log \left((0.034)/(0.07)\right ) = 2.865 + \log 0.49 = 2.865 - 0.31 = \mathbf{2.56}](https://img.qammunity.org/2021/formulas/chemistry/college/rqxzbclhx163k547ffckgbh9fkd7rjo446.png)