1.

2.5mLof 2//5M weak mono-acidic base (K_(b) = 1 xx 10^(-12) at 25^(@)C) is titrated with 2//15M HCI in water at 25^(@)C. Find the concentration of H^(o+) ions at equivalence point. (K_(w) = 1 xx 10^(-14)at 25^(@)C) a. 3.7 xx 10^(-13)M b. 3.2 xx 10^(-7)M c. 3.2 xx 10^(-2)M d. 2.7 xx 10^(-2)M

Answer»

Solution :a. First find the VOLUME of `HCI` re2uired to reach the eqivalent point.
mEq of base = mEq of HCI
`rArr (2.5 xx (2)/(5) xx 1) = ((2)/(15)xx1)V_(HCI)`
`rArr V_(HCI) = 7.5mL`
The net volume of the solution at the equivalent point
`= V_("base") +V_(HCI) = 2.5 +7.5 = 10mL`
`rArr ["salt"] = c (2//5 xx 2.5)/(10) = 0.1M`
`ph` of an aqueous solution of such a salt is given by :
`pH = 7 - (1)/(2) (pK_(b) +logC)`
`= 7-(1)/(2) (12 + log 0.1) = 1.5`
`rArr [H^(o+)] = "Antilog" (-1.5)`
`= "Antilog" [(-1-0.5 +1-1) = bar(2).5]`
`= 3.2 xx 10^(-2)M`
or
`[H^(o+)] = 10^(-15) = (1)/(10sqrt(10)) = 3.2 xx 10^(-2)M` (Answer 'c')
Please note that answer (c) of the above solution is incorrect. (Why ?)
Actually, `pH = 7 - (1)/(2) (pK_(b) + logC)` is valid only when
`1-h = 1`.
To CHECK, claculate `h` using :
`h = sqrt((K_(h))/(c)) = sqrt((K_(w))/(K_(b)C)) = sqrt((10^(-14))/(10^(-12)xx0.1)) = sqrt(0.1)`
`rArr 1 - sqrt(0.1) != 1`
So, we have to solve from basics as follows:
`{:(B^(oplus),+,H_(2)O,hArr,BOH + ,H^(oplus)),(C-Ch,,,,Ch,Ch):}`
`rArr K_(h) = ([BOH][H^(o+)])/([B^(o+)]) = ((Ch)(Ch))/(C-Ch)`
`K_(h) = (K_(w))/(K_(a)) = (10^(-14))/(10^(-12)) = 10^(-2) = 0.01`
Also,
`K_(h) = (Ch^(2))/((1-h))` (Not neglecting `h` and solving, we get)
`0.01 = (0.1 xxh^(2))/(1-h)`
or `h~~ 0.271`
`[H^(o+)] = Ch = 0.27 xx 0.1 = 0.0271 = 2.71 xx 10^(-2) M`
Hence answer is (d).
Note: In such problem, the answer cna be obtained DIRECTLY. The answer (c) `(3.2 xx 10^(-2)M)` is calculated by using the formula of salt of `W_(B)//S_(A)`. The concentration of salt is `0.1M` (which is very high). So `(1-h)` cannot be taken equal to `1`, since the two answer (c) and (d) are very close to each other. THEREFORE, `[H^(o+)]` would slightly less than the calculated value.
`:. [H^(o+)]` calculated by using formula `= 3.2 xx 10^(-2)M`
`[H^(o+)]` observed (by not using approximation) `= 2.7 xx 10^(-2)M`
In such problem, if the `pH` is asked, calculated it by using formula will be slightly less than the observed `pH` (by not using approcimation) e.g., `pH` (calculated by using formula) `=- log (3.2 xx 10^(-2))`
`=- log [(2)^(5) x 10^(-3)]`
`=-5 log 2+3 = 1.5`
`pH` (observed) (by not usingapproximation
`=- log (27 xx 10^(-3))`
`=- 3log 3+3 = 1.56`


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