강의자료 저작권 관련 유의사항 안내

“본 강의자료는 연세대학교 학생들을 위해

수업목적으로 제작ㆍ게시된 것이므로 수업목적 외
용도로 사용할 수 없으며, 다른 사람들과 공유할 수
없습니다. 위반에 따른 법적 책임은 행위자 본인에게
있습니다.”

나. 금지되는 행위
(1) 위와 같이 내려 받은 강의자료를 수강생 본인 외 제3자에게 배포(출력물의 경우), 전송(파일
업로드)하는 행위
(2) 강의자료를 수강생 외에는 (i) 이용할 수 없도록 하는 접근제한조치, (ii) 복제할 수 없도록
하는 복제방지조치를 무력화하는 행위. 예컨대 강의자료가 게시된 와이섹 등에 접근할 수 있는
아이디와 비밀번호를 타인과 공유하거나 알려주는 행위, 강의자료에 부착된 복제방지조치를
무력화하는 해킹 행위 등
(3) 특히 동영상을 포함하여 강의자료를 인터넷에 게시 또는 타인에게 전송하는 순간, 외국의
저작권 침해가 될 수 있고, 심각한 소송의 대상이 될 수 있습니다. 해당 강의자료에 외국의
저작물이 포함되어 있을 수 있고, 그것이 외국에서 접근가능한 상태가 되기 때문입니다. 따라서,
강의자료를 타인과 공유하거나 전송 및 공개하는 행위를 하여서는 안 됩니다.
 Materials Inorganic Chemistry

Chapter 6. Acid-Base and

Donor-Acceptor Chemistry

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/185p
 History
Acid-Base Reactions
: Reactions in which cations, anions, or electron pairs are transferred from
one species to another.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/170p
 Major Acid-Base Concepts
1. Arrhenius concept
- Acid: H+ donor
- Base: OH- donor

2. Bronsted-Lowry concept
- Acid: a species with a tendency to lose a hydrogen ion
- Base: a species with a tendency to gain a hydrogen ions
- Conjugate acid and base
- In any solvent, the direction of the reaction always favors the formation of
acids or bases weaker than the reactants.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/170~172p
 Solvent System Concept
- The solvent-system definition applies to any solvent that can dissociate
into a cation and an anion (autodisassociation)
- Acids: solutes that increase the concentration of the solvent cation
- Bases: solutes that increase the concentration of the solvent anion

- The solvent-system approach can also be used with solvents that do not
contain hydrogen.

- Acid-base reactions in the solvent-system concept are the reverse of

autoionization.

- Neutralization: the reaction of an acid with a base to produce a salt plus

one or more solvent molecules.
 Solvent System Concept
- Caution is needed in interpreting the reaction with negligible
autoionization.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/171p
 Lewis Concept
Lewis concept
- Acids: electron pair acceptors
- Bases: electron pair donors
- The lone pair in the HOMO of the ammonia interacts with the empty
LUMO of BF3.
- The B-F bonds in the product are bent away from the ammonia into a
nearly tetrahedral geometry around boron (coordination compounds).

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/185p
 Other Concepts of Acids and Bases
Lux-Flood (Theories Based on Anion Transfer)
- Acids: oxide ions acceptor
- Bases: oxide ions donor

Usanovich
- Any salt forming reaction can be
considered an acid-base reaction.
- Acid: any substance that forms salt
by reacting with bases, by donating
a cation, or by adding anions or electrons.
- Base: any substance that forms salt
by reacting with acids, by accepting
a cation, or by donating anions or electrons.
Nonaqueous Solvents and Acid-Base Strength
- Any acid will react with a basic solvent, and any base will react with an
acidic solvent with the extent of the reaction varying with their relative
strengths.

- Water is amphoteric with both acidic and basic properties.

- The strongest acid possible in water is hydronium ions and the

strongest base is the hydroxide ion.

- The leveling effect: acids or bases are brought down to the limiting
conjugate acid or base of the solvent.
- Acidic solvents allow separation of strong acids in order of strength.
Nonaqueous Solvents and Acid-Base Strength
- Inert solvents with neither acidic nor basic properties allow a wider
range of acid-base behavior.
 Bronsted-Lowry Superacids
- Acid solutions more acidic than sulfuric acid are called superacids.
- The acidity of superacids is frequently measured by the Hammett acidity
function. The stronger the acid, the more negative its H0.
(B: nitroaniline, BH+: its conjugate acid)
- The Lewis superacids formed by the
fluorides are a result of transfer of
anions to form complex fluoro anions.
- Water is a strong base in superacid media.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/174p
Thermodynamic Measurement in Solution
- One way to access the strengths of aqueous acids is to quantify the
enthalpy change.
- Application of Hess’s law for determining the enthalpy and entropy of the
ionization of a weak acid HA.

A plot of ln Ka vs. 1/T

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/175p
 Comparing Basicity
- Basicity: The enthalpy of proton transfer reaction between weak bases
and strong acids.

- A Bronsted basicity scale is established by measuring the enthalpy

changes associated with the protonation of weak bases in fluorosulfonic
acid (HSO3F).

- The more positive the pKBH+, the weaker the conjugate acid and the
stronger the conjugate base.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/176p
 Trends in Bronsted-Lowry Basicity
- Correlations between gas-phase and aqueous basicity data provides a
starting point to consider the importance of electronic, steric, and
solvent effects on proton transfer reactions.
- Inductive effects are useful to rationalize trends in both gas-phase and
aqueous basicity
NH3 < NH2Me < NH2Et < NHMe2 < NHEt2 < NHBu2
- The substitution of alkyl groups for hydrogen within the series of
ammonia to primary amines to secondary amines results in
progressively more electron-rich nitrogen centers and stronger
Bronsted-Lowry bases. A longer alkyl chain enhances the effect.
- The substitution of electronegative atoms or groups in place of
hydrogen on ammonia results in weaker bases.
NMe3 < NHEt2 < NHBu2 < NEt3 < NBu3
 Solvation Effects
- In aqueous solution, the methyl-substituted amines have basicities in
the order of NMe3 < NBu3 < NEt3 < NHEt2 < NHBu2
NH3 < NMe3 < NH2Me < NHMe2
NH3 < NH2Et < NEt3 < NHEt2
- In both series, the tertiary amines are weaker bases than expected,
because of the reduced solvation of their protonated cations.

- Solvation is dependent on the number of hydrogen atoms available for

hydrogen bonding to water to form hydrogen bonds. With fewer
hydrogens available for such hydrogen bonding, the more highly
substituted molecules are less basic.
- Pyridine and aniline have higher gas-phase basicities than ammonia,
but are weaker bases than NH3 in aqueous solution due to the enhanced
hydrogen bonding with NH4+.
 Steric Effects
- Steric effects are less obvious from these correlations.

- One might expect 2-t-butylpyridine to be more basic than 2-

methylepyridine on the basis of inductive effects, but the tertiary butyl
steric bulk attenuates the basicity on steric grounds by making the
nitrogen less accessible and more difficult to solvate upon protonation.

- However, small proton size renders these steric effects less important
in gauging the Bronsted-Lowry basicity of amines, whereas steric
hindrance often plays major roles in understanding Lewis
acidity/basicity.
 Acidity and Basicity of Binary
Hydrogen Compounds
- The binary hydrogen compounds range from the strong acids HCl to the
weak base NH3. Others, CH4, show almost no acid-base properties.

- Acidity increases with increasing numbers of electrons in the central atom,

either going across the table or down; but the electronegativity effects are
opposite for the two directions.

Gary L. Miessler, Paul J. Fischer, Donald A.

Tarr./Inorganic chemistry: INTERNATIONAL
EDITION /PESRSON/FIFTH EDITION/2013/182p
 Acidity and Basicity of Binary
Hydrogen Compounds
- The binary hydrogen compounds range from the strong acids HCl to the
weak base NH3, and other CH4 showing almost no basicity/acidity.
- Acidity increases with increasing numbers of electrons in the central atom,
either going across the table or down
- Acidity increases going down the series, H2Se > H2S > H2O
- The strongest acid is the largest, heaviest member.
- The conjugate bases of the larger molecules have lower charge density and
therefore a smaller attraction for hydrogen ions. As a result, the larger
molecules are stronger acids, and their conjugate bases are weaker.
- Within a period, acidity is greatest for the compounds of elements toward
the right with greater electronegativity.
- The more electronegative elements form the stronger acids. The order of
acid is NH3 < H2O < HF
- The same general trends persist when the acidity of these compounds is
measured in aqueous solution. HCl, HBr, HI are strong acid in water.
- All the other binary hydrogen compounds are weaker acids, their strength
decreasing toward the left in the periodic table.
 Bronsted-Lowry Strength of Oxyacids
- As the number of oxygen atoms increases, oxyacid strength increases.
HClO4 > HClO3 > HClO2 > HClO
- For oxyacids with multiple ionizable hydrogens, the pKa values
increase by about five units with each successive proton removal.
- The larger the number of these oxygens to share the negative charge,
the more stable and weaker the conjugate base, and the stronger the
hydrogenated acid.
- The electron density supporting O-H bond decreases with increasing
the number of oxygens. The O-H becomes more susceptible to the
cleavage.

Gary L. Miessler, Paul J. Fischer, Donald A.

Tarr./Inorganic chemistry: INTERNATIONAL EDITION
/PESRSON/FIFTH EDITION/2013/183p
Bronsted-Lowry Acidity of Aqueous Cations
- Highly oxidized metal ions forms an acidic solution via hydrolysis.
Proton transfer occurs from solvated water molecule resulting in
bound hydroxide.

- In more basic solutions, hydroxide or oxide bridges between metal atoms

form, the high positive charge promotes more hydrogen ion disassociation,
and a large aggregate of hydrated metal hydroxide precipitates.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic

chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH
EDITION/2013/184p
Acidity of Cations in Aqueous Solution
- Metal ions with larger charges and smaller radii are stronger acids.
- The alkali metal ions are not acidic. 2+ transition metal ions are
weakly acidic. 3+ transition metal ions are moderately acidic. Ions
that would have charges of 4+ and higher as monatomic ions are such
strong acids in aqueous solution.
- At the highly charged extreme, the free metal cation is no longer a
detectable species. Instead oxometalate species are formed.
- Permanganate and chromate are strong oxidants particularly in acid
solution.

- In concentrated acid, the dichromate ion is formed by loss of water.

Acidity of Conjugate Acid of Weak Base
- Salt of the conjugate acid (e.g. NH4+ cation) of weak base shows
considerable acidity due to the dissociation of cation.
(NH4)Cl -> NH4+ + Cl-: acid
NH4+ <-> NH3 + H+
- Salt of the conjugate base (e.g. OAc- anion) of weak acid shows
considerable basicity due to the dissociation of anion.
NaOAc -> Na+ + OAc-: base
OAc- + H2O <-> HOAc + OH-
Lewis Acid-Base Concept and Frontier Orbitals
Lewis concept
- Acids: electron pair acceptors
- Bases: electron pair donors
- The lone pair in the HOMO of the ammonia interacts with the empty
LUMO of BF3.
- The B-F bonds in the product are bent away from the ammonia into a
nearly tetrahedral geometry around boron (coordination compounds).

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/185p
Frontier Orbitals and Acid-Base Reactions
- The a1 orbital containing the lone pair electrons of the ammonia molecule
combines with the empty 1s orbital of the hydrogen ion to form bonding
and antibonding orbitals. The lone pair in the a1 orbital of NH3 is
stabilized by this interaction. The net result is a lowering of the energy as
the nonbonding a1 becomes a bonding t2, a result of the interaction of the
HOMO of the base NH3 and the LUMO of the acid H+.
- In most acid-base reaction, a HOMO-LUMO combination forms new
HOMO and LUMO orbitals of the product.
- A base has an electron pair in a HOMO of suitable symmetry to interact
with the LUMO of the acid. Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/186p

oxidant acid base reductant

Inductive Effects on Lewis Acidity & Basicity
- Substitution of electronegative atoms or groups in place of hydrogen
on ammonia results in weaker bases.
Gary L. Miessler, Paul J. Fischer, Donald A.
Tarr./Inorganic chemistry: INTERNATIONAL
EDITION /PESRSON/FIFTH EDITION/2013/193p

- A similar effects in the reverse directions results from substitution of

alkyl groups for hydrogen.
- These inductive effects are similar to the effects seen in organic
molecules containing electron-contributing or electron-withdrawing
groups.
- The boron halides do not follow this argument, because BF3 and BCl3
have significant p bonding that increases the electron density on boron.
- The relatively short B-F bonds in BF3 permit the previously mentioned
p bonding to partially quench some Lewis acidity at boron.
Lewis acidity: BF3 << BCl3 < BBr3 < BI3
- As the halogen atom size increases, the B-X bond lengthens and the p
interaction decreases.
 Steric Effects on Lewis Acidity & Basicity
- When bulky groups are forced together by adduct formation, their
mutual repulsion makes the reaction less favorable.
1. Front (F) strain
2. Back (B) strain
3. Internal (I) strain
- Gas-phase measurements of proton affinity show the sequence of basic
strength Me3N > Me2NH > MeNH2 > NH3.
- When larger acids are used, the order changes (e.g. BF3 and BMe3)

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic

chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH
EDITION/2013/194,195p
Intermolecular Forces-Hydrogen Bonding
Hydrogen bonding: A hydrogen bond X-H…B is formed from an attraction
between an X-H unit and a donor atom (B). The interaction can be either
intermolecular or intramolecular.
1. The polarity of X-H leads to an electrostatic contribution.
2. The donor-acceptor nature of the interaction results in partial covalent
character and charge transfer from B to X-H.
3. Dispersion forces also contribute to hydrogen bonds.
- The H…B strength increases as the electronegativity of X within the polar
covalent X-H bond increases.
IUPAC standards
1. An X-H…B angle of 180o is indicative of a relatively strong hydrogen bond.
2. The X-H infrared stretching frequency is red-shifted upon formation of X-
H…B consistent with X-H weakening and lengthening.
3. The NMR chemical shift of the proton linking X and B is a sensitive
function of the hydrogen bond strength.
4. The magnitude of DG for X-H…B is larger than thermal energy of system.
 Receptor-Guest Interaction
- Molecules having extended pi system can interact with each other to
hold molecules or portions of molecule together.
- Molecular tweezers or clips
- The product is an inclusion
complex formed by p-p interactions.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/200p
 Hard and Soft Acids and Bases
- Hard: nonpolarizable. Soft: polarizable.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/201p
 Hard and Soft Acids and Bases
- The soft iodide ions form a more covalent bonds with Ag+ ions.
(AgI: yellow, AgBr: slightly yellow, AgCl, AgF: white)
- Solubility (LiBr > LiCl > LiI > LiF). The strong hard-hard interaction
in LiF overcomes the tendency to be solvated by water.

- The class (b) are located in the lower

right-hand side of the transition metals
in periodic table.
- Many other metal are in class (b) when
they are in low or zero oxidation states.
- Solubility of class (b) (F->Cl->Br->I-)
- Solubility of class (a) (I->Br->Cl->F-)
- The class (b) metals have d electrons
available for p bonding.
- The class (b) metals have the most favorable enthalpy for the
donor molecules or ions that are readily polarizable and have
vacant d or p* available for p bonding. Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/202p
 Hard and Soft Acids and Bases
Linkage isomerism
[Hg(SCN)4]2-: a soft-soft interaction (Pd2+, Pt2+)
[Zn(NCS)4]2-: a hard-hard interaction (Ni2+, Cu2+)
- Intermediate transition metal ions can in some cases bond to either end
of thiocyanate.
[Co(NH3)5(SCN)]2+ and [Co(NH3)5(SCN)]2+
Exchange reaction
: As the halide becomes larger and more polarizable, the tendency for
attachment to soft mercury (II) grows stronger through a soft-soft
interaction.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/203p
 Theory of HSAB
- The class (a) metal: hard acids; The class (b) metal: soft acids
- Much of the hard-soft distinction depends on polarizability.
- Hard acids and bases are relatively small, compact, and nonpolarizable.
- Soft acids and bases are larger and more polarizable.
- Hard acids: large positive charge (beyond +3), d electrons relatively unavailable
for p bonding
- Soft acids: d electrons readily available for p bonding and lower oxidation state.
- The larger and more massive the atom, the softer it is likely to be.
- The class (b) ions are primarily +1 and +2 ions and are in the 4d and 5d
transition metal.
- More electrons and larger
sizes of bases lead to softer
behavior.
- The negative charge is
more available for
polarization.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/204p
 Theory of HSAB
- In addition to soft-hard nature, the inherent acid-base strength must be kept
in mind.
- The strength of the acid or base may be more important than the hard-soft
characteristics.
- In general, hard-hard combinations are more favorable energetically than
soft-soft ones.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/204p
 Theory of HSAB
- Hard-hard or soft-soft combinations lead to insoluble salts.
- HSAB explain the formation of some metallic ores (sulfide vs. oxide).
- The hard-hard interactions are considered as simple electrostatic
interactions with the LUMO of the
acid far above the HOMO of the base
and relatively little change in orbital
energies on adduct formation.
- A soft-soft interaction involves HOMO
and LUMO energies that are much closer
and gives a large change in orbital
energies on adduct formation.
- The hard-hard interactions depend on
electrostatic force.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/206p
 Quantitative Measures
Absolute hardness: half the difference between IE and EA, which is
related to the Miliken’s definition of electronegativity

- A hard acid or base are species that has a large difference between IE & EA
- Softness is the inverse of hardness.

IE : a measure of HOMO energy

EA: a measure of LUMO energy

- For the halogen, the trend in hardness

parallels the change in HOMO energies,
because the LUMO energies are nearly Gary L. Miessler, Paul J. Fischer, Donald
A. Tarr./Inorganic chemistry:

the same. (F2>Cl2>Br2>I2) INTERNATIONAL EDITION

/PESRSON/FIFTH EDITION/2013/207p
 Quantitative Measures
Drago & Wayland: electrostatic (E) and covalent (C) factors

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/208p
 Quantitative Measures

- Both E and C increase, which is contrast to most description of bonding.

- The E and C approach explains acid-base formation better than the
HSAB Theory via the provision of quantitative prediction.
- Pearson’s system: emphasis on the covalent factor, log K = SASB + sAsB
- Solvent interaction should be taken into account for predicting reaction.
Quantitative Measures

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/207p