Em có thể vào link sau để xem giải thích :
http://www.vias.org/genchem/acidbase_equ_12591_06.html
Tui chắc chắn câu một lực acid HF > HCl > HBr > HI là sai. Độ tăng lực acid được giải thích bằng năng lượng nối HX giảm dần do chênh lệch chu kỳ (row) nên sự xen phủ giữa nguyên tử H và halogen X ngày càng giảm tính hiệu quả. Trong hóa thực nghiệm, nhiều phản ứng HCl không đủ mạnh, ta phải dùng đến HBr hoặc HI.
Acid strength and Molecular Properties
Author: John Hutchinson
We now have a fairly complete quantitative description of acid-base equilibrium. To complete our understanding of acid-base equilibrium, we need a predictive model which relates acid strength or base strength to molecular properties. In general, we expect that the strength of an acid is related either to the relative ease by which it can donate a hydrogen ion or by the relative stability of the remaining negative ion formed after the departure of the hydrogen ion.
To begin, we note that there are three basic categories of acids which we have examined in this study. First, there are simple binary acids: HF; HCl; HBr; HI. Second, there are acids formed from main group elements combined with one or more oxygen atoms, such H2SO4 or HNO3. These are called oxyacids. Third, there are the carboxylic acids, organic molecules which contain the carboxylic functional group.
We consider first the simple binary acids. HCl, HBr, and HI are all strong acids, whereas HF is a weak acid. In comparing the experimental values of pKa values in table 7, we note that the acid strength increases in the order HF < HC l < HBr < HI. This means that the hydrogen ion can more readily separate from the covalent bond with the halogen atom (X) as we move down the periodic table. This is reasonable, because the strength of the H-X bond also decreases as we move down the periodic table, as shown in table 7.
Table 7: H-X Bond Strengths and pKa
Acid pKa Bond Energy [kJ/mol]
HF 3.1 567.7
HCl -6.0 431.6
HBr -9.0 365.9
HI -9.5 298.0
The decreasing strength of the H-X bond is primarily due to the increase is the size of the X atom as we move down the periodic table. We conclude that one factor which influences acidity is the strength of the H-X bond: a weaker bond produces a stronger acid, and vice versa.
In the acids in the other two categories, the hydrogen atom which ionizes is attached directly to an oxygen atom. Thus, to understand acidity in these molecules, we must examine what the oxygen atom is in turn bonded to. It is very interesting to note that, in examining compounds like R-O-H, where R is an atom or group of atoms, we can get either acidic or basic properties. For examples, NaOH is a strong base, whereas HOCl is a weak acid. This means that, when NaOH ionizes in solution, the Na-O linkage ionizes, whereas when HOCl ionizes in solution, the H-O bond ionizes.
To understand this behavior, we compare the strength of the simple oxyacids HOI, HOBr, and HOCl. The pKa's for these acids are found experimentally to be, respectively, 10.6, 8.6, and 7.5. The acid strength for HOX increases as we move up the periodic table in the halogen group. This means that the H-O bond ionizes more readily when the oxygen atom is bonded to a more electronegative atom.
We can add to this observation by comparing the strengths of the acids HOCl, HOClO, HOClO2, and HOClO3. (Note that the molecular formulae are more commonly written as HClO, HClO2, HClO3, and HClO4. We have written them instead to emphasize the molecular structure.) The pKa's of these acids are, respectively, 7.5, 2.0, -2.7, and -8.0. In each case, the molecule with more oxygen atoms on the central Cl atom is the stronger acid: HOClO is more acidic than HOCl, etc. A similar result is found in comparing the oxyacids of nitrogen. HONO2, nitric acid, is one of the strong acids, whereas HONO, nitrous acid, is a weak acid. Since oxygen atoms are very strongly electronegative, these trends add to our observation that increasing electronegativity of the attached atoms increases the ionization of the O-H bond.
Why would electronegativity play a role in acid strength? There are two conclusions we might draw. First, a greater electronegativity of the atom or atoms attached to the H-O in the oxyacid apparently results in a weaker H-O bond, which is thus more readily ionized. We know that an electronegative atom polarizes bonds by drawing the electrons in the molecule towards it. In this case, the Cl in HOCl and the Br in HOBr must polarize the H-O bond, weakening it and facilitating the ionization of the hydrogen. In comparing HOCl to HOClO, the added oxygen atom must increase the polarization of the H-O bond, thus weakening the bond further and increasing the extent of ionization.
A second conclusion has to do with the ion created by the acid ionization. The negative ion produced has a surplus electron, and the relative energy of this ion will depend on how readily that extra electron is attracted to the atoms of ion. The more electronegative those atoms are, the stronger is the attraction. Therefore, the OCl- ion can more readily accommodate the negative charge than can the OBr- ion. And the OClO- ion can more readily accommodate the negative charge than can the OCl- ion.
We conclude that the presence of strongly electronegative atoms in an acid increases the polarization of the H-O bond, thus facilitating ionization of the acid, and increases the attraction of the extra electron to the negative ion, thus stabilizing the negative ion. Both of these factors increase the acid strength. Chemists commonly use both of these conclusions in understanding and predicting relative acid strength.
The relative acidity of carbon compounds is a major subject of organic chemistry, which we can only visit briefly here. In each of the carboxylic acids, the H-O group is attached to a carbonyl C=O group, which is in turn bonded to other atoms. The comparison we observe here is between carboxylic acid molecules, denoted as RCOOH, and other organic molecules containing the H-O group, such as alcohols denoted as ROH (R is simply an atom or group of atoms attached to the functional group). The former are obviously acids whereas the latter group contains molecules which are generally extremely weak acids. One interesting comparison is for the acid and alcohol when R is the benzene ring, C6H5. Benzoic acid, C6H5COOH, has pKa = 4.2, whereas phenol, C6H5OH, has pKa = 9.9. Thus, the presence of the doubly bonded oxygen atom on the carbon atom adjacent to the O-H clearly increases the acidity of the molecule, and thus increases ionization of the O-H bond.
This observation is quite reasonable in the context of our previous conclusion. Adding an electronegative oxygen atom in near proximity to the O-H bond both increases the polarization of the O-H bond and stabilizes the negative ion produced by the acid ionization. In addition to the electronegativity effect, carboxylate anions, RCOO-, exhibit resonance stabilization.
The resonance results in a sharing of the negative charge over several atoms, thus stabilizing the negative ion. This is a major contributing factor in the acidity of carboxylic acids versus alcohols.
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