Question

Arrange the following in the decreasing order of acidity :
(i) (1) `n-`Butanol
(2) Methy1 alcohol
(3) sec-Butanol
(4) rert-Butanol
(ii) (1) `HCOOH`
(2) `CH_3 COOH`
(3) `C_2H_5COOH`
(4) `C_6H_5 COOH`
(5) `(CH_3)_2CHCOOH`
(6) `CH_2 C1COOH`
(iii) (1) `CH_3 CH_2CH_2COOH`
(2) `CH_3 CH_2 CHC1COOH`
(3) `CH_3 CHC1CH_2COOH`
(4) `CH_2 C1CH_2 CH_2 COOH`
(iv) (1) `CH_3COOH`
(2) `CH_2C1COOH`
(3) `CHC1_2 COOH`
(4) `C C1_3 COOH`
(v) (1) `CH_3BrCOOH`
(2) `CH_2C1COOH`
(3) `CH_2 FCOOH`
(4) `CH_2 ICOOH`
(vi) (1) `C_6H_5 COOH`
(2) `p-OHC_6 H_4COOH`
(3) `p-CH_3C_6H_4COOH`
(4) `p-C1C_6H_4COOH`
(5) `p-Br C_6H_4COOH`
(6) `p-BO_2C_6 H_4 COOH`
(vii) (1) o-Hydroxybenzoic acid
(2) p-Hydroxybenzoic acid
(3) `2,6-`Dihydroxybenzoic acid.
(viii) (1) `HCOOH`
(2) `C_6 H_5 COOH`
(3) `C_6H_5OH`
(4) `HC1`
(ix) `RCOOH`
(2) `ROH`
(3) `RH`
(4) `NH_3`
(5) `HOH`
(6) `CH -= CH`
(x) (1) Phenol
(2) p-Chlorophenol
(3) p-Nitrophenol
(4) m-Cresol
(xi) (1) Phenol
(2) m-Chlorophenol
(3) m-Nitrophenol
(4) m-Cresol
(xii) (1) Phenol
(2) Benzoic acid
(3) p-Nitrophenol
(4) Carbonic acid
(xiii) (1) Phenol
(2) Benzyl alcohol
(3) Benzene sulphonic acid
(4) Benzoic acid
(xiv) (1) Phenol
(2) p-Chlorophenol
(3) 2,4,-Dichlorophenol
(4) 2,4,6-Trichlorophenol
(xv) (1) Nitroform `HC(NO_2)_3`
(2) Cyanoform `HC(CN)_3`
(3) `CHC1_3`
(xvi) (1) `CH_3 SO_2CH_3`
(2) `CH_3NO_2`
(xvii) (1) `CH_3 BO - O^(Ө)`
(2) `CH_3CHO`
(3) `CH_3 COOR`.

Answer 1

(i)
(ii) `6 gt 1 gt 4 gt 2 gt 3 gt 5` (In `(6) -I` effect of `C1 gt (1)` (standard) `gt (4)+R gt -I` of `Ph gt (2) + I`effect of `Me gt (3) + I` effect of `Et gt (5) + I` effect of two `Me` groups) .
(iii) `2 gt 3 gt 4 gt1` (2) `- I` effect of `C1` at `alpha-C gt (3) - I` effect of `C1` at `beta - C gt (4) - I` effect of `C1` at `gamma-C gt (1) + I` effect of `CH_3 CH_2 CH_2`.
(iv) `4 gt 3 gt 2 gt 1` (4) `-I` effect of `3 C1` at `alpha-C gt` (2) `-I` effect of `1 C1` at `alpha-C gt (1) + I` effect of `(CH_3 - )` group
(v) `3 gt 2 gt 1 gt 4 ` (3) `- I` effect of `F = (2) - I` effect of `C1 gt (1) - I` effect of `Br gt (4) - I` effect of `I`
(vi) `6 gt 4 gt 5 gt 1 gt 3 gt 2` (6) `-1` and `-R` effect of `(-NO_2)` group `gt (4) - I` effect of `C1 gt (5) - I` effect of `Br gt (1)` standard `gt (3) + I` and `H.C` effect of `CH_3- at p- gt`
(2) `- I` and `-R` effect of `OH` group at `p-` However, the net effect is more `overline e-`donating than the net effect of `(3)`, since `+R gt + I` and `H.C` effects.
(vii) `3 gt 1 gt 2` (3) Intramolecular H-bonding from two sides `gt (I)` Intramolecular H-bonding from one sides `gt (2) - I` and `+R` effects of `OH` group at `p-`position , net effect is `overline e-`donating.
(viii) `4 gt 1 gt 2 gt 3` (4) Inorganic acid `gt (1)` Formic acid (standard) `gt (2)` Benzonic acid, `- I` and `+R` of `Ph` group, net `overline e-`donating `gt (3)` Phenol.
(ix) `1 gt 5 gt 2 gt 6 gt 4 gt 3 gt ` (I) Acid `gt (5) H_2 O gt (2)` Alcohol `gt (6) HC -= CH`
(sp character) `gt (4) nH_3 gt (3)` Alkane (`sp^3` character)
(x) `3 gt 2 gt 1 gt 4` (3) `- NO_2(- I` and `-R` effects of `C1` at `p-) gt (2) - C1 - I` effects of `C1` at `p- gt (1)` Standard (phenol) `gt(4) CH_3 + I` effected of `CH_3` at `m-`position.
(xi) `3 gt 2 gt 1 gt 4` (3) `(-NO_2)` (only `-I` effect of `(-NO_2)` at `m-) gt (2) - C1 (-I` effected of `C1` at `m-) gt (1)` Standard (phenol) gt
`(4) Ch_3` (only `+1` effect of `CH_3` at `m-`position.
(xi) `2 gt 4 gt 3 gt 1` (2) Benzoic acid `gt (4)` Weak inorganic acid `gt (3)` Nitro phenol `(-NO_2) (-I` and `-R` effect of `(-NO_2)` at `p- ) gt (1)` phenol.
(xiii) `3 gt 4 gt 1 gt 2` (3) Sulphonic acid, `-I` and `-R` effects of `(-SO_3 H)` group `gt (4)`, Benzoic acid, `- I` and `-R` effects of `(-COOH)` group, but `(-SO_3 H)` effect `gt (-COOH)` effect `gt (1) `Phenol `gt (2)` Alcohol)
(xiv) `4 gt 3 gt 2 gt 1` (4) `- I` effect of `3 C1 gt (3) - I` effect of `2 C1 gt (2) - I` effect of `1 C1 gt (1)` Phenol, standard
(xv) `1 gt 2 gt 3` (1) `-I` effect of three `NO_2` groups `gt (2) - I` effects of three `CN` groups `gt (3) - I` effect of three `C1` groups , ` - I` effect of : `-NO_2 gt - CN gt - C1`.
(xvi) ` 2 gt 1 (2) -NO_2 (-I` effect of `NO_2 ) gt (1) - I` effect `SO_2` and `+ I` effect of two `CH_3` groups.
(xvii) `1 gt 2 gt 3` (1) `-I` effect of `-NO_2 gt (2) -I` effect of `- CHO gt (3) - I` effect of `(- COOR)` group) , `-I` effect of : `- NO_2 gt -CHO gt -COOR`.