Asam dan Basa

Topik yang akan dibahas:

• Definisi asam dan basa;
• Konsep pasangan asam-basa konjugat dari Bronsted;
• Penentuan [H3O+], [OH-], dan pH untuk asam kuat dan basa
kuat;
• Penentuan [H3O+], [OH-], pH, Ka, atau Kb, dan persen ionisasi
untuk asam lemah dan basa lemah;
• Memprediksi sifat asam/basa dari garam (senyawa ionik) dan
oksida logam dan bukan logam;
• Pengaruh struktur molekul dan energi ikatan pada kekuatan
asam dan basa.
 Asam dan Basa
• Definisi Arrhenius:
Asam: zat yang meningkatkan [H3O+] dalam larutan;
Basa: zat yang meningkatkan [OH-] dalam larutan;
• Definisi Brønsted-Lowry:
Asam: reaktan yang mendonasikan proton dalam suatu reaksi;
Basa: reaktan yang menerima proton dalam suatu reaksi;
• Definisi Lewis: - dalam pembentukan ikatan
kovalen,
Asam: salah satu yang menerima pasangan elektron
Basa: yang menyumbangkan pasangan elektron
 Asam Kuat dan Lemah
• Asam kuat terionisasi sempurna dalam larutan air:
• HCl(aq) + H2O  H3O+(aq) + Cl-(aq);
• H2SO4(aq) + H2O  H3O+(aq) + HSO4-(aq);

• Asam lemah terionisasi hanya sebagian dalam larutan

air:
• HF(aq) + H2O ⇌ H3O+(aq) + F-(aq);
• HOCl(aq) + H2O ⇌ H3O+(aq) + ClO-(aq).
Ionisasi Sempurna Asam Klorida
Disosiasi asam kuat dan lemah
 Basa Kuat dan Lemah
• Basa kuat terionisasi sepenuhnya dalam larutan air:
NaOH(aq)  Na+(aq) + OH-(aq);
Ba(OH)2(aq)  Ba 2+
(aq)
-
+ 2 OH (aq);
• Basa lemah terionisasi sebagian dalam larutan air:
NH3(aq) + H2O  NH4+(aq) + OH-(aq);
PO43-(aq) + H2O  HPO42-(aq) + OH-(aq)
Brønsted-Lowry: Asam & Basa Konjugasi

• Perhatikan kesetimbangan berikut:

HA + B ⇌ BH+ + A-;
Asam1 Basa2 Asam konjugasi2 Basa konjugasi1
• A- adalah basa konjugasi untuk asam HA;
HA dan A- adalah pasangan asam-basa konjugasi;
• BH+ adalah asam konjugasi dari basa B;
BH+ dan B juga merupakan pasangan asam-basa konjugasi.
Reaksi Asam-Basa Brønsted-Lowry
Pasangan Asam-Basa Konjugasi Brønsted
Contoh Pasangan Asam Basa Konjugasi
HNO3 – NO3-
H2SO4 – HSO4-
H3O+ – H2O
HF – F-
H3PO4 – H2PO4-
CH3COOH – CH3COO-
H2PO4- – HPO42-
NH4+ – NH3
H2O – OH-
 Latihan # 1: Asam & Basa Konjugasi

Tuliskan rumus basa konjugasi untuk asam berikut:

(a) H2CO3 (b) HSO4- (c) Al(H2O)63+
(d) Cr(OH)3(H2O)3
 Latihan # 1: Asam & Basa Konjugasi

Tuliskan rumus basa konjugasi untuk asam berikut:

(a) H2CO3 (b) HSO4- (c) Al(H2O)63+
(d) Cr(OH)3(H2O)3

(Answer: (a) HCO3-; (b) SO42-; (c) Al(H2O)5(OH)2+;

(d) Cr(OH)4(H2O)2-)
 Latihan #2: Asam dan Basa Konjugasi

Tuliskan rumus asam konjugat untuk basa berikut:

(a) NH3 (b) CO32- (c) C5H5N (d)
Al(OH)3(H2O)3
 Latihan #2: Asam dan Basa Konjugasi

Tuliskan rumus asam konjugat untuk basa berikut:

(a) NH3 (b) CO32- (c) C5H5N (d)
Al(OH)3(H2O)3

Answer: (a) NH4+; (b) HCO3-; (c) C5H5NH+;

(d) Al(OH)2(H2O)4+)
 Kekuatan Asam dan Konstanta Ionisasi
Untuk kesetimbangan ionisasi atau disosiasi asam dalam
larutan air, seperti:
HA (aq) + H2O → H3O+(aq) + A-(aq);
Konstanta ionisasi atau disosiasi dinyatakan sebagai
berikut: [H 3O  ][A - ]
Ka 
[HA]

Nilai Ka menunjukkan kekuatan relatif asam. Asam kuat

memiliki Ka yang sangat besar, sedangkan asam lemah
memiliki Ka yang kecil (Ka << 1)
 Kekuatan Relatif Asam dan Basa
Konjugatnya
Asam Basa konjugasi
Sangat kuat Sangat lemah
Kuat Lemah
Lemah Kuat
Sangat lemah Sangat kuat
• Asam kuat sangat mudah kehilangan proton → basa
konjugasi lemah;
• Asam lemah tidak mudah kehilangan proton → basa
konjugasi kuat.
Kekuatan Relatif Asam dan Basa Konjugatnya
 Sifat Asam Basa dari Air
• Air secara otomatis terionisasi menjadi:
2H2O  H3O+(aq) + OH-(aq)
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25oC

• Air terionisasi menghasilkan H3O+ and OH-, sehingga

air memiliki sifat asam dan basa. Kw disebut
konstanta ionisasi air
• Air murni pd suhu 25°C: [H3O+]=[OH-]=1.0 x 10-7 M
 Ekspresi Keasaman dalam skala pH
• pH = -log[H+] (note: [H+] = [H3O+])

• pOH = -log[OH-]
• pKw = -log(Kw); pKa = -log(Ka); pKb = -log(Kb)
• Untuk air, Kw = [H3O+][OH-] = 1.0 x 10-14
• -log(Kw) = -log [H3O+] + (-log[OH-])
• pKw = pH + pOH = 14.00
• At 25oC, pOH = 14 – pH
 Keasaman dan Rentang pH

• Larutan asam:
[H3O+] > 1.0 x 10-7 M;
pH < 7;
• Larutan basa:
[OH-] > 1.0 x 10-7 M or [H3O+] < 1.0 x 10-7 M
pH > 7;
• Larutan netral:
[H3O+] = [OH-] = 1.0 x 10-7 M; pH = 7.00
Hubungan antara keasaman larutan dan pH
pH untuk benda-benda Rumah Tangga
Household Substances
 [H3O+] dan pH Asam Kuat

• Asam kuat seperti HCl dan HClO4 terionisasi

sepenuhnya dalam larutan air:
HCl(aq) + H2O → H3O+(aq) + Cl-(aq);
HClO4(aq) + H2O → H3O+(aq) + ClO4- (aq);
• Dalam larutan asam monoprotik kuat HA,
seperti HCl dan HClO4,
[H3O+] = [HA]0
• Misalnya, pada 0,10 M HCl, [H3O+] = 0,10 M,
dan pH = -log (0,10) = 1,00
 [OH-] dan pH Basa Kuat

• Seperti asam kuat, basa kuat juga terionisasi sempurna

dalam larutan air.
Contoh: NaOH(aq) → Na+(aq) + OH-(aq);
Ba(OH)2(aq) → Ba2+(aq) + 2OH- (aq);
• Dalam larutan basa seperti 0,050 M NaOH,
[OH-] = [NaOH]0 = 0,050 M;
pOH = -log (0,050 M) = 1,30; pH = 14,00-1,30 = 12,7
• Dalam larutan basa seperti 0,050 M Ba(OH) 2,
[OH-] = 2 x [Ba(OH)2]awal = 0,10 M;
pOH = -log (0,10) = 1,00; pH = 14.00 - 1.00 = 13.00
 [H3O+] dan pH Asam Lemah

• Dalam larutan asam lemah, [H3O+] <<

[HA]0;
• Berapa [H3O+] dan pH dapat dihitung dari
konsentrasi awal asam dan nilai Ka-nya.
• Misalnya, dalam asam asetat (CH3COOH)
0,100 M, dengan Ka = 1,8 x 10-5, [H3O+] dan
pH dapat dihitung menggunakan tabel
“ICE”.
 Tabel ICE untuk Asam Asetat
• Ionization: CH3CO2H + H2O  H3O+ + CH3CO2-
• 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
• 
 
[H 3O ][CH 3CO 2 ] x2
Ka    1.8 x 10 -5
[CH 3COOH] (0.100 - x )
Menghitung [H3O+] dari konsentrasi awal dan Ka
dengan metode aproksimasi.
• Memecahkan x dalam ekspresi untuk Ka:

[H 3O  ][CH 3CO 2 ] x2
Ka    1.8 x 10 -5
[CH 3CO 2 H] (0.100 - x )
K a  [HA]0 (1.8 x 10 -5  0.100)  x  0.100,
x2 x2
and (0.10 - x ) ~ 0.10. This makes ~  1.8 x 10 -5 ;
(0.100 - x ) 0.100
x 2  (0.100)(1. 8 x 10 -5 )  1.8 x 10 -6 ; and x  1.8 x 10 -6  1.34 x 10 -3 ;
[H 3O  ]  x  1.34 x 10 -3 M; pH  - log(1.34 x 10 -3 )  2.873
 Perhitungan Persen Ionisasi
[HA]ionized x
% Ionization   100%  x 100
[HA]initial (0.100 - x )
• Kita menghitung dalam 0.10 M CH3COOH,
konsentrasi asam yang terionisasi adalah 1.34 x 10-3 M.
• Persen ionisasi 0.10 M asam asetat:
1.34 x 10 -3 M
% ionization ~ x 100%  1.34%
0.100
 Peningkatan Persen Ionisasi dengan
Pengenceran
• Persen ionisasi asam lemah meningkat dengan
meningkatnya pengenceran.
• Contohnya, jika [CH3COOH]awal = 0.01 M
• [CH3COOH]terionisasi ~ 4.24 x 10-4 M (dihitung
menggunakan metode aproksimasi);

4.24 x 10 -4
Percent ionization  x 100  4.24%
0.0100
 Persen Ionisasi Meningkat dengan
Pengenceran
• Pada [CH3COOH]awal = 0.001 M,
• [CH3COOH]terionisasi = 1.34 x 10-4 M (by approximation)

1.34 x 10 -4
Percent ionization  x 100  13.4%
0.00100
• Semakin banyak kita mengencerkan larutan asam,
semakin tinggi fraksi asam yang akan terionisasi,
yang meningkatkan derajat ionisasi.
• Apakah ini terkait dengan prinsip Le Chatelier?
Menjelaskan.
 Latihan # 3: pH dan Persen Ionisasi

1) Asam nitrat, HNO2, memiliki Ka = 4.0 x 10-4 at

25°C. Hitunglah pH dan persen ionisasi HNO2
dalam larutan asam 0.10 M.
(Answer: pH = 2.20; % ionization = 6.3%)
2) Asam klorit, HOCl, memiliki Ka = 3.5 x 10-8 at
25°C. Hitunglah pH dan persen ionisasi HOCl
dalam larutan asam 0.10 M.
(Answer: pH = 4.23; % ionization = 0.059%)
 Latihan # 3: pH dan Persen Ionisasi

1) Asam nitrat, HNO2, memiliki Ka = 4.0 x 10-4 at

25°C. Hitunglah pH dan persen ionisasi HNO2
dalam larutan asam 0.10 M.

2) Asam klorit, HOCl, memiliki Ka = 3.5 x 10-8 at

25°C. Hitunglah pH dan persen ionisasi HOCl
dalam larutan asam 0.10 M.
 [OH-] dan pH Basa Lemah

• Dalam basa lemah, [OH-] << [Basa]0;

• Berapa nilai [OH-] dan pH dapat dihitung dari
konsentrasi awal basa dan nilai Kb-nya.
• Misalnya, dalam 0,100 M amonia, NH3, dengan Kb =
1,8 x 10-5, [OH-] dan pH dapat dihitung menggunakan
tabel “ICE” berikut.
 Tabel ICE untuk Ionisasi Amonia

• Ionization: NH3 + H2O  NH4+ + OH-

• 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
• 

[NH 4 ][ OH - ] x2
Kb    1.8 x 10 5
[NH 3 ] (0.100  x )
Menghitung [OH-] dari konsentrasi awal dan Kb
dengan metode aproksimasi.
• Menyelesaikan x pada ekspresi untuk Kb:
[NH 4 ][ OH - ] x2
Kb    1.8 x 10 5
[NH 3 ] (0.100  x )
K b  [B] 0 (1.8 x 10-5  0.100)  x  0.100, and
x2 x2
(0.100 - x ) ~ 0.100, which makes ~  1.8 x 10-5 ;
(0.100 - x ) 0.100
x 2  (0.100)(1.8 x 10-5 )  1.8 x 10-6 , which yields x  1.34 x 10-3 ;
[OH - ]  1.34 x 10-3 M  pOH  2.873, and pH  11.127
 Latihan # 4: pH Basa Kuat dan Lemah

1) Ethylamine, C2H5NH, memiliki Kb = 5.6 x 10-4.

Hitunglah konsentrasi H3O+ dalam larutan
ethylamine 0.10 M dan pH larutan?

2) Pyridine, C5H5N, memiliki Kb = 1.7 x 10-9.

Hitunglah konsentrasi H3O+ dalam larutan pyridine
0.020 M dan pH larutan?
 Latihan # 4: pH Basa Kuat dan Lemah

1) Ethylamine, C2H5NH, memiliki Kb = 5.6 x 10-4.

Hitunglah konsentrasi H3O+ dalam larutan
ethylamine 0.10 M dan pH larutan?
(Answer: [H3O+] = 1.3 x 10-12 M; pH = 11.87)

2) Pyridine, C5H5N, memiliki Kb = 1.7 x 10-9.

Hitunglah konsentrasi H3O+ dalam larutan pyridine
0.020 M dan pH larutan?
(Answer: [H3O+] = 1.7 x 10-9 M; pH = 8.77)
 Asam Poliprotik
• Adalah asam dengan lebih dari satu ion hidrogen yang
dapat terionisasi, seperti H2SO3, H2SO4, H3PO4,
H3C6H5O7, etc.
• Hidrogen terionisasi secara bertahap, misalnya,
H3PO4(aq) + H2O ⇄ H3O+(aq) + H2PO4-(aq); Ka1 = 7.5 x 10-3
H2PO4-(aq) + H2O ⇄ H3O+(aq) + HPO42-(aq); Ka2 = 6.2 x 10-8
HPO42-(aq) + H2O ⇄ H3O+(aq) + PO43-(aq); Ka3 = 4.8 x 10-13
• Kekuatan asam menurun dengan urutan: H3PO4 >>
H2PO4- >> HPO42-;
• pH dari larutan ditentukan sebagian besar oleh ionisasi
dari H3PO4
 Latihan # 5: pH H2SO4

1) Hitunglah konsentrasi H2SO4, H3O+, HSO4-, dan

SO42-, dalam larutan H2SO4 0.10 M. Berapakah pH
larutan? (H2SO4 adalah asam kuat dan HSO4-
mempunyai Ka = 1.2 x 10-2)

(Answer: [H2SO4] = 0.0 M; [H3O+] = 0.11 M;

[HSO4-] = 0.090 M; [SO42-] = 0.0098
M;
pH = 0.96]
 Garam dan Asam & Basa Terkaitnya

• Asam dan basa tempat masing-masing garam berikut

diproduksi.
Acids Bases
• NaClO4
• KNO3
• (NH4)2SO4
• NaC2H3O2
• BaCl2
• Na3PO4
 Sifat Asam Basa Larutan Garam

• Garam-garam yang larut akan terdisosiasi

sepenuhnya saat dilarutkan dalam air;
• Ion yang dihasilkan dapat bereaksi dengan air
yang melepaskan H3O+ dan membuat larutan
menjadi asam, atau menghasilkan OH- dan
membuat larutan menjadi basa.
 Sifat Asam Basa Larutan Garam

• Sifat asam-basa dari larutan garam bergantung pada

apakah senyawa tersebut merupakan produk dari:
1. Reaksi asam kuat-basa kuat: menghasilkan garam netral
2. Reaksi asam kuat-basa lemah: menghasilkan garam
asam
3. Reaksi asam lemah-basa kuat: menghasilkan garam
basa
4. Reaksi basa lemah-asam lemah: menghasilkan garam
yang bersifat asam atau basa, tergantung pada kekuatan
relatif asam dan basa.
 Jenis Garam dan Solusinya
• Garam Reaksi Asam Kuat-Basa Kuat:
NaCl, NaNO3, KBr, dll .; larutan ber-pH netral
• Garam Reaksi Basa Kuat-Asam Lemah:
NaF, NaNO2, NaC2H3O2, dll .; larutan bersifat basa
• Garam Reaksi Asam Kuat-Basa Lemah:
NH4Cl, NH4NO3, (CH3)2NH2Cl, C5H5NHCl; Larutan garam
ini bersifat asam
• Garam Reaksi Asam Lemah-Basa Lemah:
NH4C2H3O2, NH4CN, NH4NO2, dll. Senyawa ini dapat
bersifat asam, basa, atau netral, yang bergantung pada
kekuatan relatif asam dan basa.
 Garam hasil reaksi Asam Kuat-Basa Kuat

• Disosiasi dan reaksi garam netral :

NaCl(aq)  Na+(aq) + Cl-(aq);
Na+(aq) + H2O  tidak bereaksi
Cl- (aq) + H2O  tidak bereaksi
(Konsentrasi H3O+ dan OH- dalam larutan NaCl
sama dengan dalam larutan air murni → adalah
netral.)
 Garam hasil Reaksi Basa Kuat-Asam Lemah

• Disosiasi dan reaksi garam basa:

NaNO2(aq)  Na+(aq) + NO2-(aq);
Na+(aq) + H2O  tidak beraksi
NO2-(aq) + H2O  HNO2(aq) + OH-(aq)

(Reaksi NO2- dengan air menyebabkan [OH-] >

[H3O+] dan larutan menjadi basa.)
 Garam Reaksi Asam Kuat-Basa Lemah

• Dissociation and reaction of an acidic salt:

NH4NO3(aq)  NH4+(aq) + NO3-(aq);
NH4+(aq) + H2O  NH3(aq) + H3O+(aq);
NO3-(aq) + H2O  tidak bereaksi;
• Reaksi NH4+ dengan air menyebabkan [H3O+]>[OH-],
dan larutan menjadi asam
 Garam Reaksi Asam Lemah-Basa Lemah

Garam yang dihasilkan oleh reaksi asam lemah dan basa

lemah dapat bersifat netral, asam, atau basa, tergantung
pada besaran relatif Ka dari asam lemah dan Kb dari basa
lemah.
Jika Ka ~ Kb, garamnya netral; contoh: NH4C2H3O2
Jika Ka > Kb, garam bersifat asam; contoh: NH4NO2
Jika Ka < Kb, maka garam adalah basa; contoh:
NaC2H3O2
 Memprediksi Properti Asam-Basa Garam

• Perhatikan larutan yang mengandung NH4C2H3O2

• NH4C2H3O2(aq) → NH4+(aq) + C2H3O2-(aq);
• NH4+(aq) + H2O → H3O+(aq) + NH3(aq);
Ka = 5.6 x 10-10
• C2H3O2-(aq) + H2O → HC2H3O2(aq) + OH-(aq);
Kb = 5.6 x 10-10
• Ka = Kb = 5.6 x 10-10, → NH4C2H3O2 adalah netral
 Memprediksi Properti Asam-Basa Garam

• Perhatikan larutan yang mengandung (NH4)2SO4

• (NH4)2SO4(aq) → 2NH4+(aq) + SO42-(aq);
• NH4+(aq) + H2O → H3O+(aq) + NH3(aq);
Ka = 5.6 x 10-10
• SO42-(aq) + H2O → HSO4-(aq) + OH-(aq);
Kb = 8.3 x 10-13
• Ka > Kb → (NH4)2SO4 adalah asam
Memprediksi Karakter Asam-Basa suatu Garam

• Perhatikan larutan yang mengandung NH4CN.

• NH4CN(aq) → NH4+(aq) + CN-(aq);
• NH4+(aq) + H2O → H3O+(aq) + NH3(aq);
Ka = 5.6 x 10-10
• CN-(aq) + H2O → HCN(aq) + OH-(aq);
Kb = 1.6 x 10-5
• Kb > Ka → NH4CN adalah basa
 Pengaruh Struktur pada Sifat Asam-Basa

• Kekuatan ikatan relatif:

H─F > H─Cl > H─Br > H─I
• Kekuatan asam relatif:
HI > HBr > HCl > HF
(HF adalah satu-satunya asam lemah dalam grup ini)
• Kekuatan asam relatif:
H2Te > H2Se > H2S > H2O (all very weak
acids)
 Pengaruh Struktur pada Sifat Asam-Basa

Efek Elektronegatifitas pada Kekuatan Relatif Asam-Oxo:

Atom pusat yang sama, tetapi jumlah atom oksigen berbeda:
HOClO3> HOClO2 > HOClO> HOCl;
Jumlah oksigen yang sama, tetapi atom pusatnya berbeda:
1. Tren elektronegativitas: F> Cl> Br> I;
2. Kecenderungan keasaman relatif: HOF> HClO> HOBr> HOI;
3. Keasaman relatif: CF3COOH> CCl3COOH> CH3COOH
4. Tren elektronegativitas: Cl > S > P > Si
5. Keasaman relatif: HClO4 > H2SO4 > H3PO4 > H4SiO4
 Sifat Asam-Basa Oksida

• Oksida logam bersifat basa atau amfoter

• Oksida basa:
Na2O(s) + H2O  2NaOH(aq)  2Na+(aq) + 2OH-(aq);
MgO(aq) + HCl(aq)  MgCl2(aq) + H2O
• Oksida amfoter:
Al2O3(s) + HCl(aq)  2AlCl3(aq) + H2O
Al2O3(s) + 2NaOH(aq) + 3H2O  2NaAl(OH)4(aq)
 Sifat Asam-Basa Oksida

• Oksida non logam adalah asam;

N2O5 + H2O  2HNO3(aq);
SO3(g) + H2O  H2SO4(aq);
Cl2O7 + H2O  2HClO4(aq)
• Kecenderungan:
Keasaman meningkat dari kiri ke kanan selama suatu periode
SiO2 < P4O10 < SO3 < Cl2O7
Keasaman menurun dari atas ke bawah dalam tabel periodik
N2O5 > P4O10 > As2O5 > Sb2O5
 Sifat Asam-Basa Oksida

• Tren sifat asam-basa oksida dalam tabel

periodik: dari yang paling basa (di sebelah
kiri) sampai yang paling asam (di sebelah
kanan):
Na2O, MgO, Al2O3, SiO2, P4O10, SO3, Cl2O7
• Tren sifat asam basa turun satu kelompok:
paling asam di kiri ke paling basa di kanan:
N2O5, P4O10 , As2O5, Sb2O5
 Asam dan Basa Lewis

• Identifikasi asam Lewis dan basa Lewis dalam reaksi

berikut:
(a) H2O + CO2(aq)  H2CO3(aq);
(b) Cu2+(aq) + 4NH3(aq)  Cu(NH3)42+(aq);
(c) AlCl3 + Cl-  AlCl4-;
(d) BF3 + NH3  F3B─NH3
 Kesetimbangan Asam-Basa
• Efek Ion Umum dalam Asam dan Basa
• Larutan Buffer untuk Mengontrol pH
• Kapasitas Buffer
• Kurva pH-Titrasi
• Indikator Titrasi Asam-Basa
 Efek Ion Umum
• Pergeseran posisi kesetimbangan karena
penambahan ion yang sudah terlibat dalam
proses kesetimbangan.
• Penerapan prinsip Le Châtelier.
 Efek Ion Umum

Pertimbangkan keseimbangan berikut:

• HC2H3O2(aq) + H2O(l) ⇌ H3O+(aq) + C2H3O2-(aq)
• Menambahkan NaC2H3O2 ke larutan akan menggeser
kesetimbangan ke kiri karena [C2H3O2-] meningkat; C2H3O2-
adalah bagian dari sistem kesetimbangan.
• Pergeseran kesetimbangan ini menyebabkan [H3O+] menurun
dan menaikkan pH larutan.
• Larutan yang mengandung campuran HC2H3O2 dan
NaC2H3O2 kurang asam dibandingkan larutan HC2H3O2 saja,
dan kurang basa dibandingkan larutan NaC2H3O2 saja.
pH of weak acid and the Effect of Common

Consider the following solutions:

• Calculate the pH of 1.00 M HC2H3O2 solution.
• What is the pH of a solution that contains 1.00 M
HC2H3O2 and 0.50 M NaC2H3O2.
Solution-1:
Equilibrium: HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-(aq)

Initial [ ], M 1.00 0.00 0.00
Change, D[ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x x

 pH of Acetic Acid by itself.
• Solution-1:

[H 3O  ][CH 3CO 2 ] x2
Ka    1.8 x 10 -5
[CH 3COOH] (1.00 - x )

• By approximation, x = (1.00 x 1.8 x 10-5 )  4.2 x 10-3

• [H3O+] = x = 4.2 x 10-3 M,  pH = 2.37

 Acetic Acid-Acetate Equilibrium

Solution-2:

Equilibrium: HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-

(aq)

Initial [ ], M 1.00 0.00 0.50
Change, D[ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x (0.50 + x)

 pH of Acetic Acid + Sodium Acetate

Solution-2:

[H 3O  ][CH 3CO 2 ] ( x )( 0.50  x )
Ka    1.8 x 10 -5
[CH 3COOH] (1.00 - x )

By approximation,
x = (1.00/0.50)(1.8 x 10-5) = 3.6 x 10-6 M
[H+] = x = 3.6 x 10-6 M,  pH = 4.44

Solution containing HC2H3O2 and NaC2H3O2 is less acidic

than one containing only HC2H3O2 at the same concentration.
Solving Problems with Buffered Solutions
Buffering: How Does It Work?
Buffering: How Does It Work?
Buffer Solutions
 Henderson–Hasselbalch Equation

• HA(aq) ⇌ H+(aq) + A-(aq);

 
• Ka = [ H ][ A ]
[ HA ]
• pH = pKa + log([A–]/[HA])
• For a particular buffer system, solutions
with the same [A–]/[HA] ratio have same pH.
 pH of Buffer Solution: example #1

• What is the pH of a buffer solution that is 0.45 M

acetic acid (HC2H3O2) and 0.85 M sodium acetate
(NaC2H3O2)? The Ka for acetic acid is 1.8 × 10–5.

• Solution:
• pH = pKa + log([C2H3O2-]/[HC2H3O2]
• pH = -log(1.8 × 10–5) + log(0.85/0.45)
• pH = 4.74 + 0.28 = 5.02
 Characteristics of Buffer Solutions

• Contain weak acids or weak bases and their

corresponding conjugate partners (common ions).
• Resist changes in pH.
• Buffering capacity depends on concentrations of
weak acid or weak base and their common ions.
• Effective pH buffering range ~ pKa  1
 Characteristics of Buffer Solutions
1. Buffers contain relatively large amounts of the weak acids
(HA) and their conjugate base (A‫)־‬, (or weak bases and their
conjugate acids)
2. Buffer pH is determined by the pKa of the acid HA and the
molar ratio of the conjugate base to acid: [A‫]־‬/[HA].
3. Buffer pH changes very little because the ratio [A‫]־‬/[HA]
changes very little when a small amount of strong acid or
strong base is added.
4. [H3O+] in buffer solutions remains more or less constant:
Most of H+ from strong acid is absorbed by the conjugate
base A‫ ;־‬most of OH‫ ־‬added from strong base reacts with
acid HA in the buffer to yield A‫ ־‬and H2O.
 Buffering Capacity
• How much H3O+ or OH- the buffer can absorb
without significantly changing its pH.
• Depends on the concentrations of HA and A‫־‬.
• High [HA] and [A‫ ]־‬lead to large buffering capacity.
• Optimal buffering occurs when [HA] = [A‫;]־‬
• Ratio [A–] / [HA] ~ 1 strong resist to change when
either H3O+ or OH– is added.
 Some Common Buffers

Buffers pKa pH Range

• HCHO2 – NaCHO2 3.74 2.74 – 4.74
• CH3CO2H – NaCH3CO2 4.74 3.74 – 5.74
• KH2PO4 – K2HPO4 7.21 6.20 – 8.20
• CO2/H2O – NaHCO3 6.37 5.40 – 7.40
• NH4Cl – NH3 9.25 8.25 – 10.25

 Choosing a Buffer System
• The weak acid in buffer has pKa close to target pH.
• For example, KH2PO4 and K2HPO4 may be used to
buffer at pH ~ 7.5 (H2PO4‫ ־‬has pKa = 7.20)
• Phosphate buffer is most effective in the pH range
6.20 – 8.20; it has the highest buffering capacity at
about pH = 7.20.
Making Buffer Solution: example #2

A phosphate buffer with pH = 7.40 is prepared

using KH2PO4 and K2HPO4.
(a) What is the molar ratio of [HPO42-] to [H2PO4-]
in the buffered solution?
(b) If [H2PO4-] = 0.20 M, what is [HPO42-]?
(c) How many grams of KH2PO4 and K2HPO4,
respectively, are needed to make 500. mL of this
solution? (H2PO4- has Ka = 6.2 x 10-8)
 Solutions to Buffer example #2

(a) Use Henderson-Hasselbalch equation:

• pH = pKa + log([HPO42-]/[H2PO4-])
• 7.40 = 7.21 + log([HPO42-]/[H2PO4-])
• log([HPO42-]/[H2PO4-]) = 7.40 – 7.21 = 0.19
• [HPO42-]/[H2PO4-] = 100.19 = 1.55

(b) If [H2PO4-] = 0.20 M,

• [HPO42-] = 1.55 x 0.20 M = 0.31 M
 Solutions to Buffer example #2

(c) Moles of KH2PO4 needed =

500. mL x (1 L/1000 mL) x 0.20 mol/L = 0.10 mole
• Moles of K2HPO4 needed =
500. mL x (1 L/1000 mL) x 0.31 mol/L = 0.155 mole
• Grams of KH2PO4 needed =
0.10 mol x (136.086 g/mol) = 14 g
• Grams of K2HPO4 needed =
0.155 mol x (174.178 g/mol) = 27 g
 Buffer Exercise #1

Indicate whether each of the following mixtures

makes a buffer solution. Explain.
(a) 50.0 mL of 0.20 M CH3CO2H + 50.0 mL of 0.20 M
NaCH3CO2;
(b) 50.0 mL of 0.20 M HC2H3O2 + 50.0 mL of 0.10 M NaOH;
(c) 50.0 mL of 0.20 M HC2H3O2 + 50.0 mL of 0.20 M NaOH;
(d) 50.0 mL of 0.20 M NaC2H3O2 + 50.0 mL of 0.20 M HCl;
(e) 50.0 mL of 0.20 M NaC2H3O2 + 50.0 mL of 0.10 M HCl

(Answer: (a) Yes; (b) Yes; (c) No; (d) No; (e) Yes)
 Buffer Exercise #2
Indicate whether each of the following solution
mixtures will make a buffer solution. Explain.
(a) 50.0 mL of 0.10 M NH3 + 50.0 mL of 0.10 M NH4NO3;
(b) 50.0 mL of 0.10 M NH3 + 50.0 mL of 0.10 M HNO3;
(c) 50.0 mL of 0.10 M NH3 + 25.0 mL of 0.10 M HNO3;
(d) 50.0 mL of 0.10 M NH4NO3 + 25.0 mL of 0.10 M NaOH;
(e) 50.0 mL of 0.10 M NH4NO3 + 50.0 mL of 0.10 M NaOH;

(Answer: (a) Yes; (b) No; (c) Yes; (d) Yes; (e) No)
 Buffer Exercise #3

An acetate buffer solution is prepared by mixing

35.0 mL of 1.0 M acetic acid and 65.0 mL of 1.0 M
sodium acetate. (a) What is the pH of this solution?
(b) If 0.010 mole of HCl is added to this solution
without altering its volume, what will be the pH of
the resulting solution? (Ka = 1.8 x 10-5)

(Answer: (a) pH = 5.01; (b) pH = 4.83 after adding 0.10 M HCl)

 Buffer Exercise #4

The Ka values of some acids and base are given below:

1. Acetic acid, CH3CO2H, Ka = 1.8 x 10-5;
2. Dihydrogen phosphate, H2PO4‫־‬, Ka = 6.2 x 10-8;
3. Ammonia, NH3, Kb = 1.8 x 10-5;
4. Hydrogen carbonate, HCO3‫־‬, Kb = 2.3 x 10-8.

What solutions are used to make buffers with the

following pH’s?
(i) pH = 7.00; (ii) pH = 4.50; (iii) pH =
9.00 (iv) pH = 9.50; (v) pH = 5.00
 Buffer Exercise #5

How many milliliters of each solution of 0.50 M

KH2PO4 and 0.50 M K2HPO4 are needed to make
100.0 mL solution of phosphate buffer with pH =
7.50? What are the final concentrations of K+, H2PO4-
and HPO42-, in the buffer solution?
(for H2PO4-, Ka = 6.2 x 10-8)

(Answer: (a) 33.9 mL of KH2PO4 + 66.1 mL of K2HPO4;

(b) [K+] = 0.83 M; [H2PO4-] = 0.17 M; [HPO42-] = 0.33 M)
 Titration and pH Curves
• Plotting the pH of the solution being analyzed as a
function of the amount of titrant added.
• From pH-titration curve determine the equivalence
point – when enough titrant has been added to react
exactly with the substance in solution being titrated.
The pH Curve for the Titration of 50.0 mL of
0.200 M HNO3 with 0.100 M NaOH
The pH Curve for the Titration of 100.0 mL of
0.50 M NaOH with 1.0 M HCI
The pH Curve for the Titration of 50.0 mL of
0.100 M HC2H3O2 with 0.100 M NaOH
The pH Curves for
the Titrations of
50.0-mL Samples
of 0.10 M Acids
with Various Ka
Values with 0.10
M NaOH
The pH Curve for the Titration of 100.0mL of
0.050 M NH3 with 0.10 M HCl
 Acid-Base Indicators

• An indicator is a substance added to acid or

base solution to marks the end point of a
titration by the change of its color.
For example, phenolphthalein changes from
colorless to pink at the end point when an acid is
titrated with a base.
• The end point of a titration should correspond
to the equivalence points of the acid-base
reaction.
The Acid and
Base Forms of
the Indicator
Phenolphthalein
The Methyl Orange Indicator is Yellow in Basic
Solution and Red in Acidic Solution
 Choosing Indicators
1. The pH range for color changes should occur
within the sharp vertical rise (or drop) in the
pH-titration curves.
2. An indicator changes color at pH = pKa ± 1,
where pKa is that of the indicator used.
pH Ranges for Indicators
 Common Indicators

Indicators: Acid Base pH Range Type of Titration
Color Color

1. Methyl orange Orange Yellow 3.2 – 4.5 strong acid-strong base
strong acid-weak base
2. Bromocresol Yellow Blue 3.8 – 5.4 strong acid-strong base
green strong acid-weak base
3. Methyl red Red Yellow 4.5 – 6.0 strong acid-strong base
strong acid-weak base
4. Bromothymol Yellow Blue 6.0 – 7.6 strong acid-strong base
blue
5. Phenol Red Orange Red 6.8 – 8.2 strong acid-strong base
weak acid-strong base

Useful pH Ranges for Several Common Indicators
 Calculating the pH of solution during titration

Strong Acid-Strong Base Titration;

1. Net reaction: H3O+(aq) + OH-(aq)  2H2O
2. Determine the limiting reactant and calculate the
final concentration of H3O+ or OH- that is in excess.
3. Calculate pH using concentration of excess H3O+ or
OH-
 Titration Problem: example #1
A 20.0 mL aliquot of 0.100 M HCl is titrated with
0.100 M NaOH solution. What is the pH of the
resulting solution after 15.0 mL of NaOH has been
added?

Reaction: H3O+(aq) + OH-(aq)  2H2O

[I]before rxn: 0.057 M 0.043 M
[C]from rxn: -0.043 M -0.043 M
[E]after rxn: 0.014 M 0.000

pH = -log(0.014) = 1.85
 pH of Weak Acid-Strong Base Titrations

Net reaction: HA(aq) + OH-(aq)  H2O + A-(aq);

1. Assume the reaction with OH- goes to completion;
2. If OH- is the limiting reactant:
(mol of HA)final = (mol of HA)initial – (mol of OH-);
(mol of A-)final = (mol of OH-)
3. [HA]final = (mol of HA)final/Vfinal;
4. [A-]final = (mol A-)final/Vfinal
5. pH = pKa + log([A-]f/[HA]f)
 Titration Problem: example #2

Weak Acid-Strong Base Titration:

• A 20.0 mL aliquot of 0.100 M HNO2 is titrated with
0.100 M NaOH. (a) What is the pH of the solution
before titration? (b) What is the pH of the solution
after 15.0 mL of NaOH has been added? (c) What is
the pH of the solution at equivalent point (after 20.0
mL of 0.100 M NaOH is added)?
(Ka of HNO2 = 4.0 x 10-4)
 Solution to Titration Problem: example #2

(a) Solving initial concentration of H3O+ by

approximation method:
[ H 3O  ]  [HNO 2 ] x K a  (0.100 x 4.0 x 10 -4  0.0063 M

pH = -log(0.0063) = 2.20
 Solution to Titration Problem: example #2

(b) Concentrations after 15.0 mL of NaOH is added:

Reaction: HNO2(aq) + OH-(aq)  NO2-(aq) + H2O
[I]before rxn: 0.057 M 0.043 M 0.000
[C]from rxn: -0.043 M -0.043 M +0.043 M
[E]after rxn: 0.014 M 0.000 0.043 M

• pH = pKa + log([NO2-]f/[HNO2]f)
• = -log(4.0 x 10-4) + log(0.043/0.014)
• = 3.40 + 0.49 = 3.89
 Solution to Titration Problem: example #2

(c) Calculating pH at equivalent point:

Reaction: HNO2(aq) + OH-(aq)  NO2-(aq) + H2O
[I]before rxn: 0.050 M 0.050 M 0.000
[C]from rxn: -0.050 M -0.050 M +0.050 M
[E]after rxn: 0.000 M 0.000 0.050 M

• At equivalent point, [NO2-] = 0.050 M

• Kb for NO2- = Kw/Ka = (1.0 x 10-14)/(4.0 x 10-4)
= 2.5 x 10-11
 Solution to Titration Problem: example #2

(c) Calculating pH at equivalent point (continue):

• Set up the following equilibrium for the reaction of
NO2- with water:
• Reaction: NO2-(aq) + H2O ⇄ HNO2 + OH-(aq);
[I]before rxn: 0.050 M 0.000 0.000
[C]from rxn: -x +x +x
[E]after rxn: (0.050 – x) x x
 Solution to Titration Problem: example #2
(c) Calculating pH at equivalent point
(continue):

Kb = x2/(0.050 – x) = 2.5 x 10-11

• x = [OH-],
• Using

approximation method, -11
[OH ]  [NO 2 ] x K b  (0.050 x 2.5 x 10
-
 1.1 x 10 -6 M

• pOH = -log(1.1 x 10-11) = 5.95

• pH = 14.00 – 5.95 = 8.05
 pH of Strong Acid-Weak Base Titrations

Net reaction: B(aq) + H3O+(aq)  BH+(aq) + H2O;

1. Assume the reaction with H3O+ goes to completion;
2. If H3O+ is the limiting reactant, at the end of the
reaction, (mol B)final = (mol B)initial – (mol H3O+);
3. (mol BH+)final = (mol H3O+)
4. [B]final = (mol B)final/Vfinal;
5. [BH+]final = (mol BH+)final/Vfinal
6. pH = pKa + log([B]f/[BH+]f; (pKa is for BH+)
 Titration Problem: example #3

Strong Acid-Weak Base Titration:

• A 20.0 mL aliquot of 0.100 M NH3 is titrated with
0.100 M HCl. (a) What is the pH of the solution
before titration? (b) What is the pH of the solution
after 10.0 mL of HCl has been added? (c) What is the
pH of the solution at equivalent point (after 20.0 mL
of 0.100 M HCl is added)?
(Kb of NH3 = 1.8 x 10-5)
 Solution to Titration Problem: example #3

(a) Solving initial concentration of OH- by

approximation method:
[OH - ]  [ NH 3 ] x K b 
 (0.100 x 1.8 x 10 -5 )  1.3 x 10 -3 M
[H3O+] = Kw/[OH-] = (1.0 x 10-14)/(1.3 x 10-3)
= 7.5 x 10-12 M
pH = -log(7.5 x 10-12 M) = 11.13
 Solution to Titration Problem: example #3

(b) Concentration after 10.0 mL of HCl is added:

Reaction: NH3(aq) + H3O+(aq)  NH4+(aq) + H2O
[I]before rxn: 0.067 M 0.033 M 0.000
[C]from rxn: -0.033 M -0.033 M +0.033 M
[E]after rxn: 0.034 M 0.000 0.033 M

• pH = pKa + log([NH3]f/[NH4+]f)
• = -log(5.6 x 10-10) + log(0.034/0.033)
• = 9.25 + (0.0) = 9.25
 Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point:

Reaction: NH3(aq) + H3O+(aq)  NH4+(aq) + H2O
[I]before rxn: 0.050 M 0.050 M 0.000
[C]from rxn: -0.050 M -0.050 M +0.050 M
[E]after rxn: 0.000 M 0.000 0.050 M

• At equivalent point, [NH4+] = 0.050 M

• Ka for NH4+ = Kw/Kb = (1.0 x 10-14)/(1.8 x 10-5)
= 5.6 x 10-10
 Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point (continue):

• Set up the following equilibrium for the reaction of
NO2- with water:
• Reaction: NH3(aq) + H3O+(aq)  NH4+(aq) + H2O
[I]before rxn: 0.050 M 0.000 0.000
[C]from rxn: -x +x +x
[E]after rxn: (0.050 – x) x x
 Solution to Titration Problem: example #3

(c) Calculating pH at equivalent point (continue):

Ka = x2/(0.050 – x) = 5.6 x 10-10

• x = [H3O+],
• Using approximation method,

[H 3O  ]  [NH 4 ] x K a
 (0.050 x (5.6 x 10 -10 )  5.3 x 10 -6 M
• pH = -log(5.3 x 10-6 = 5.28
 Titration Exercise #1

25.0 mL of 0.10 M HCl is titrated with 0.10 M NaOH

solution. (a) What is the pH of the acid before NaOH
solution is added? (b) What is the pH after 15.0 mL of
NaOH solution is added? (c) What is the pH of the
solution after 25.0 mL of NaOH is added?

(Answer: (a) pH = 1.00; (b) pH = 1.60; (c) pH = 7.00)

 Titration Exercise #2

25.0 mL of 0.10 M acetic acid is titrated with 0.10 M

NaOH solution. (a) What is the pH of the acid
solution before NaOH is added? (b) What is the pH
after 15.0 mL of NaOH solution is added? (c) What is
the pH after 25.0 mL of NaOH is added?

(Answer: (a) pH = 2.87; (b) pH = 4.92; pH = 8.72)

 Titration Exercise #3

25.0 mL of 0.10 M lactic acid, HC3H5O3, is titrated

with 0.10 M NaOH solution. After 15.0 mL of NaOH
is added, the solution has pH = 4.03. (a) Calculate the
Ka of lactic acid. (b) What is the initial pH of 0.10 M
lactic acid before NaOH is added?

(Answer: (a) Ka = 1.4 x 10-4; (b) pH = 2.43)