Acid - Base c ng, m m. Acid c ng: Cation ho c phn t c kch th bi n d ng.

c nh , m t

i n tch d

ng cao, kh b

Acid m m ng c l i, c kch th c l n, d b phn c c, d nh n e. VD: Acid c ng: H+, Ca2+, Al3+ Acid m m: Cu+, Ag+, GaCl3. Base c ng: Ation ho c phn t c kch th c nh , kh b bi n d ng. Base m m ng c l i: Kch th c l n, d b phn c c, d cho e. VD: Base c ng: F-, Cl-, OH-, NH3. Base m m: I-, CN-, C2H4. ? Cc acid hay base cng kh cho-nh n e v cng kh bi n d ng th cng c ng ? C cc acid base khng c ng, khng m m. Quy t c ph n ng: Cc acid c ng d ph n ng v i base c ng t o cc h p ch t b n, t ng t cho cc acid/base m m. Ch n m t acid ho c m t base lm chu n, xc nh b n cc h p ch t t o thnh c a n v cc acid/base khc so snh c ng. VD: c ng t ng d n trong dy base sau: Te2+ c ng t ng d n trong dy acid sau: Ag+ nh gi kh n ng t x y ra c a ph n ng acid - base b ng m nh acid - base c a ch t Nguyn t c nh gi: Tnh acid - base c a cc ch t tham gia ph n ng cng khc xa nhau, ph n ng cng d x y ra v x y ra cng hon ton. m nh acid - base c a ch t ph thu c vo: - B n ch t c a nguyn t t o acid hay base - S oxy ha c a nguyn t t o acid hay base -Tr ng thi c u t o c a ch t. - Mi tr ng x y ra ph n ng. nh gi m nh acid - base theo b n ch t c a nguyn t t o acid hay base Nguyn t c tnh kim lo i cng m nh th h p ch t cng c tnh base, nguyn t c tnh phi kim lo i cng m nh th h p ch t c a n cng c tnh acid. nh gi m nh acid - base theo m c oxi ha c a nguyn t t o acid hay base i v i h p ch t cng lo i m t nguyn t , m c oxi ha c a nguyn t t ng th tnh acid

c a h p ch t t ng. V d : So snh tnh acid v tnh base c a dy: MnO - Mn2O3 - MnO2 - Mn2O5 - MnO3 - Mn2O7 MnO :Oxit base, tan d dng trong acid long. Mn2O3 v MnO2: Oxit l ng tnh, tnh acid v tnh base u r t y u. Mn2O7 : l anhidrit c a acid m nh (HMnO4 ; pK = -2,3). Vi t ph n ng minh h a trn c s tnh acid - base *V MnO c tnh base tr i nn d tan trong dung d ch acid long: a) MnO(r) + 2HCl(dd) = MnCl2(dd) + H2O *V MnO2 c tnh base r t y u nn ch tan ch m trong acid c nng: 1b) MnO2(r) + 4HCl( c, nng) = MnCl4(dd) + H2O Tuy nhin v ion Mn4+ l ch t oxy ha r t m nh nn MnCl4 ti p t c ph n ng n i oxy ha kh 2b) MnCl4(dd) = MnCl2 + Cl2(k) K t qu b) MnO2(r) + 4HCl( c, nng) = MnCl2(dd) + Cl2(k) + H2O *Mn2O7 l m t oxiacid m nh do n d dng ph n ng v i n c c ng nh v i dung d ch base long c) Mn2O7(r) + H2O(l nh) = 2HMnO4 (dd) d) Mn2O7(r) + 2NaOH(dd) = 2NaMnO4(dd) + H2O nh gi m nh acid - base theo kh n ng ph n ng v i dung mi c a nguyn t t o acid hay base V d : Xt m nh c a Ca(OH)2 trong dung d ch n c Ca l kim l ai ki m th chu k 4, phn nhm IIA, l kim lo i r t m nh, c m i n 1,0, c th kh chu n (?o) b ng -2,76V, v v y c th d on Ca(OH)2 l m t base m nh i n ly hon ton trong n c. Tuy nhin Ca(OH)2 b n v ng (?Go298 = -898kJ/mol; ?Ho298 = -986 kJ/mo)l nn tan trong n c c a Ca(OH)2 nh : 0,1620 v 0,14830, v v y th c t Ca(OH)2 l m t base ch c m nh trung bnh. (Dung d ch bo ha canxi hydroxit 30oC c pH ? 0,9) nh gi m nh acid - base theo mi tr ng x y ra ph n ng So snh m c th y phn c a mu i nhm sulfat khi khng c v c m t ion florua (l y d ) T (Al(OH)3) = 1.10-32, Kkb([AlF6]3-) = 1.10-20,67, KHF = 1.10-3,18 Khi khng c ion F-: Al3+.aq + 3H2O = Al(OH)3 ? + 3H+.aq Kcb* = K3H2O/TAl(OH)3 = 1.10-10

Khi c m t ion F-: [AlF6]3-.aq + 3H2O = Al(OH)3? + 3HF+ 6FKcb** = Kkb. K3H2O/TAl(OH)3.K3HF = 1. 10-21,13 Khi khng c ion F- , ion Al3+ th y phn g p : Kcb*/Kc** = 1.10-10/1.10-21,13 = 1.1011,13 l n

Ralph Pearson
Hard' applies to species which are small, have high charge states (t p trung) , and are weakly polarizable. ( phn c c)

Hard acids and hard bases tend to have the following characteristics:
y y y y y

small atomic/ionic radius (bn knh) high oxidation state (b c oxi ha cao) low polarizability ( phn c c y u) high electronegativity hard bases have highest-occupied molecular orbitals (HOMO) of low energy, and hard acids have lowest-unoccupied molecular orbitals (LUMO) of high energy.[7][8]

Examples of hard acids are: H+, light alkali ions (Li through K all have small ionic radius), Ti4+, Cr3+, Cr6+, BF3. Examples of hard bases are: OH, F, Cl, NH3, CH3COO, CO32. The affinity of hard acids and hard bases for each other is mainly ionic in nature.
'Soft' applies to species which are big, have low charge states and are strongly polarizable.

Soft acids and soft bases tend to have the following characteristics:
y y y y y

large atomic/ionic radius low or zero oxidation state high polarizability low electronegativity soft bases have HOMO of higher energy than hard bases, and soft acids have LUMO of lower energy than hard acids. (However the soft-base HOMO energies are still lower than the soft-acid LUMO energies.)[7][8]

Examples of soft acids are: CH3Hg+, Pt2+, Pd2+, Ag+, Au+, Hg2+, Hg22+, Cd2+, BH3. Examples of soft bases are: H, R3P, SCN, I. The affinity of soft acids and bases for each other is mainly covalent in nature.

CH3Hg+, Hydroxide OHHydride Hg2+, Hg22+ Alkali metals Li+,Na+,K+ Platinum Pt2+ Alkoxide ROThiolate 4+ 2+ Titanium Ti Palladium Pd Halogens F ,Cl Halogens 3+ 6+ + Chromium Cr ,Cr Silver Ag Ammonia NH3 Phosphine Boron BF3 borane BH3 Carboxylate CH3COO- Thiocyanate trifluoride Pcarbon Carbocation R3C+ Carbonate CO32chloranil monoxide bulk M0 Hydrazine N2H4 Benzene Metals Gold Au+ Table 1. Hard and soft acids and bases Hydronium H+ Mercury

HRSIPR3 SCNCO C6H6

Chemical hardness in electron volt Acids Bases + Hydrogen H infinite Fluoride F- 7 Aluminum Al3+ 45.8 Ammonia NH3 6.8 + Lithium Li 35.1 hydride H- 6.8 Scandium Sc3+ 24.6 carbon monoxide CO 6.0 Sodium Na+ 21.1 hydroxyl OH- 5.6 Lanthanum La3+ 15.4 cyanide CN- 5.3 Zinc Zn2+ 10.8 phosphane PH3 5.0 Carbon dioxide CO2 10.8 nitrite NO2- 4.5 Sulfur dioxide SO2 5.6 Hydrosulfide SH- 4.1 Iodine I2 3.4 Methane CH3- 4.0 Table 2. Chemical hardness data [9]