
Concept explainers
Interpretation:
The pH during the titration of 10.00 mL of 0.400 M hypochlorous acid with 0.500 M KOH after the addition of 0%, 50%,95%,100%, and 105% of the base needed to reach the equivalence point has to be calculated. The titration curve has to be drawn and four regions of importance have to be labeled.

Explanation of Solution
The volume of base required to reach the equivalence point can be calculated as given below.
N1V1=N2V2V1=N2V2N1=0.400 M×10 mL0.500 M=8 mL
The addition of 0%, 50%, 95%, 100%, and 105% of the base needed to reach the equivalent point means 0%, 50%, 95%, 100%, and 105% of 8 mL.
0%×8 mL=0 mL50%×8 mL=4 mL95%×8 mL=7.6 mL100%×8 mL=8 mL105%×8 mL=8.4 mL
Addition of 0 mL of 0.500 M NaOH to 10.00 mL of 0.400 M HOCl:
HOCl is a weak acid. The initial point in the titration when the base is not added to the system, the system is a weak acid system.
The iCe table can be set up to calculate the pH of the solution.
HOCl+H2O⇌H3O++OCl−i(M)0.40000C(M)−y+y+ye(M)0.400−yyy
The Ka value for HOCl is 4.0×10−8. The expression for Ka can be written as given below,
Ka=[H3O+][OCl−][HOCl]=4.0×10−8y2(0.400−y)=4.0×10−8
This can be solved by approximation. If y≪0.400, then
y2≈4.0×10−8×0.400=1.6×10−8y=√1.6×10−8=1.26×10−4=[H3O+]
The pH of the solution can be calculated as given below.
pH=−log[H3O+]=−log(1.26×10−4)=3.89.
Addition of 4 mL of 0.500 M NaOH to 10.00 mL of 0.400 M HOCl:
The neutralization reaction can be written as given,
HOCl(aq)+OH−(aq)→OCl−(aq)+H2O(l)
Calculation of milimole of acid and base:
Amount of HOCl=10.00 mL×(0.400 milimol H3O+mL)=4 milimolAmount of OH−=4.00 mL×(0.500 milimol OH−mL)=2 milimol
Making of sRfc table:
The table can be formed as shown below.
The molar ratio of acid and base is 1:1. So the limiting reactant is OH− ion.
HOCl+OH−→OCl−+H2Os(mmol)420ExcessR(mmol)−2−2+2+2f(mmol)202Excess
All the strong base is consumed. There are weak acid (HOCl) and its conjugate base (OCl−) in the solution. So this solution is a buffer. By using Henderson-Hasselbalch equation, it’s pH can be calculated.
pH=pKa+lognbna=pKa+log22=pKa+0=pKa=−log(Ka)=−log(4.0×10−8)=7.34
Addition of 7.6 mL of 0.500 M NaOH to 10.00 mL of 0.400 M HOCl:
Calculation of milimole of acid and base:
Amount of HOCl=10.00 mL×(0.400 milimol H3O+mL)=4 milimolAmount of OH−=7.6 mL×(0.500 milimol OH−mL)=3.8 milimol
Making of sRfc table:
The table can be formed as shown below.
The molar ratio of acid and base is 1:1. So the limiting reactant is OH− ion.
HOCl+OH−→OCl−+H2Os(mmol)43.80ExcessR(mmol)−3.8−3.8+3.8+3.8f(mmol)0.203.8Excess
All the strong base is consumed. There are weak acid (HOCl) and its conjugate base (OCl−) in the solution. So this solution is an acidic buffer. By using Henderson-Hasselbalch equation, it’s pH can be calculated.
pH=pKa+lognbna=pKa+log3.80.2=pKa+1.278=−log(Ka)+1.278=−log(4.0×10−8)+1.278=7.34+1.278=8.62.
Addition of 8 mL of 0.500 M NaOH to 10.00 mL of 0.400 M HOCl:
Calculation of milimoles of acid and base and total volume:
Amount of HOCl=10.00 mL×(0.400 milimol H3O+mL)=4 milimolAmount of OH−=8 mL×(0.500 milimol OH−mL)=4 milimolTotal volume=18 mL
Making of sRfc table:
The table can be formed as shown below.
The molar ratio of acid and base is 1:1.
HOCl+OH−→OCl−+H2Os(mmol)440ExcessR(mmol)−4−4+4+4f(mmol)004Excessc(M)000.2222Excess
Both H3O+ and OH− ions have been completely consumed, the titration is at the equivalence point. There is only the conjugate base and water in the solution.
The iCe table can be set up to calculate the pH of the solution.
OCl−+H2O⇌HOCl+OH−i(M)0.222200C(M)−y+y+ye(M)0.2222−yyy
The expression for Kb can be written as given below,
Kb=[HOCl][OH−][OCl−]=y2(0.2222−y)
The value of Kb can be calculated as given below.
Kb=KwKa=1.0×10−144.0×10−8=0.25×10−6
This can be solved by approximation. If y≪0.2222, then
y2≈0.25×10−6×0.2222=0.056×10−6y=√0.056×10−6=2.4×10−4=[OH−]
The pH of the solution can be calculated as given below.
pOH=−log[OH−]=−log(2.4×10−4)=3.62pH+pOH=14pH=14−pOH=14−3.62=10.38
Addition of 8.4 mL of 0.500 M NaOH to 10.00 mL of 0.400 M HOCl:
Calculation of milimoles of acid and base and total volume:
Amount of HOCl=10.00 mL×(0.400 milimol H3O+mL)=4 milimolAmount of OH−=8.4 mL×(0.500 milimol OH−mL)=4.2 milimolTotal volume=18 .4mL
Making of sRfc table:
The table can be formed as shown below.
The molar ratio of acid and base is 1:1. So the limiting reactant is H3O+ ion.
HOCl+OH−→OCl−+H2Os(mmol)44.20ExcessR(mmol)−4−4+4+4f(mmol)00.24Excessc(M)00.0110.217Excess
Now, the pH of the system can be calculated as given below.
pOH=−log[OH−]=−log(0.011)=1.96pH+pOH=14pH=14−pOH=14−1.96=12.04
Titration curve:
The titration curve is plotted between volume of base added and the corresponding pH values.
Volume of NaOH(mL)pH03.8947.347.68.62810.388.412.04
The titration curve with four important regions is given below.
Figure
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