MINISTRY OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF TECHNICAL AND VOCATIONAL EDUCATION

E.Ch-01011 ENGINEERING CHEMISTRY

A.G.T.I(First Year)

(Textile & Metallurgy)

PART ONE

CHAPTER 1 1. Atoms and Atomic theory

1.1 Dalton's Atomic Theory 1. Each chemical element is composed of minute, indestructible particles called atoms. Atoms can neither be created nor destroyed during a chemical change. 2. All atoms of the elements are alike in mass (weight) and other properties, but the atoms of one element are different from those of all other elements. 3. In each of their compounds, different elements combine in a simple numerical ratio: for example, one atom of A to one of B (AB), or one atom of A to two of B (AB2), 0r....... 1.2 The Discovery of Electrons In passing electricity through evacuated glass tubes, Faraday discovered cathode rays, a type of radiation emitted by the negative terminal or cathode that cross the evacuated tube to the positive terminal or anode. cathode rays travel in straight lines and have properties that are independent of the cathode material (i.e., whether it is iron, platinum, etc.); cathode rays are invisible and are deflected by electric and magnetic fields in the manner expected for negatively charged particles. Thomson concluded that cathode rays are negatively charged fundamental particles of matter found in all atoms and become known as electrons.
Metal shield with slid Cathod green beam of light anode

(-)
fluorescent screen High voltage source

(+)

1.3 X-rays and Radioactivity X-rays: X-ray is a form of high-energy electromagnetic radiation.

 Radioactivity: Radioactivity is a natural phenomenon that is spontaneous emission of radiation by mineral sources. Three types of radiation from radioactive materials: Alpha rays (): are particles carrying two fundamental units of positive charge and having the same mass as He atom. Beta rays (): are negatively charged particles produced by changes occurring within the nuclei of radioactive atoms and have the same properties as electrons. Gamma rays (): penetrating power. 1. are electromagnetic radiation of extremely high

1.4 Rutherford's atomic model; (the nuclear atom) Most of the mass and all of the positive charge of an atom are centered in a very small region called the nucleus. The atom is mostly empty space. The magnitude of the positive charge is different for different atoms and is approximately one half the atomic weight of the element. There exist as many electrons outside the nucleus as there are units of positive charge on the nucleus. The atom as a whole is electrically neutral. Characteristic properties of fundamental particles of matter Particle Mass Charge 1.5 Isotopes Two or more atoms having the same atomic number (Z) but different mass numbers (A) are called isotopes. 20 For example, 10 Ne,1021Ne, 22Ne are the three neon isotopes. 10 The atomic mass Proton (p) 1 amu Positive (+1) Neutron (n) 1 amu Neutral Electron (e-) 1/1840 amu Negative (-1)

2. 3.

The atomic mass (weight) of an element is the average of the isotopic masses, weighted according to the naturally occurring abundances of the isotopes of the element.
mass of fractional mass of at. mass fractional of an = Example:abundance of x isotope + abundance of x isotope + ... (1) isotope (2) (2) element isotope (1)

The mass transfer of carbon shows that 98.892% of carbon atoms are carbon-12 with a mass of 12 u, exactly, and 1.108% are carbon-13 with a mass of 13.00335 u. Example: 1.1 Solution: contribution to fraction of all x mass 12C atom 12 = 12 at. mass by C atoms that are C = 0.9889 x 12.0000 u = 11.867 u contribution to fraction of all x mass 13C atom 13 = 13 at. mass by C atoms that are C = 0.01108 x 13.00335 u = 0.1441 u at. mass of naturally occurring carbon = (contribution by 12C) + (contribution by13C) = 11.867 u + 0.1441 u = 12.011 u. 1.6 The Avogadros num er (or) Avogadros constant The number of atoms in exactly 12 g of pure carbon-12 (12C) is called Avogadros number (or) constant. Its numeral value is 6.02x1023. 1.7 The concept of mole: (The mole) The mole is the amount of substance that consists of a number of chemical units equal to the number of atoms in exactly 12 units of pure carbon-12. The mass of one mole of atoms of a pure element in grams is numerically equal to the atomic weight of that element in amu. Calculate the atomic mass of carbon.

For instance, a pure sample of the metallic element titanium (Ti) shoes atomic weight is 47.88 amu is taken and measure out 47.88 g of it, you will have one mole (or) 6.023x1023 atoms of titanium. Example: 1.2 How many 24Mg atoms are present in 8.27x10-3 mol Mg ? Solution:
24

Mg atoms = 8.27x10-3 mol Mg x = 4.981 x 1021 atoms

6.023x1023 atoms
1 mol Mg

Example: 1.3 How many Pb atoms are present in a small piece of lead with a volume of 0.105 cm3 ? The density of Pb solution = 11.34 g/cm3, (Pb = 207) Solution: Conv: Vol. g. Pb mol. Pb 11.34 g Pb 1 cm solution
3

atoms. Pb x 1 mol. Pb 207 g.Pb

Pb atoms = 0.105 cm3 x =

6.023x1023 atoms
1 mol Pb

= 3.4645 x 1021 atoms of Pb. CHAPTER 2. 2. Structure of Atom

2.1 Electromagnetic radiation: Electromagnetic radiation is a form of energy transmission through a vacuum (empty space) or a medium (such as glass) in which electric and magnetic fields are propagated as waves. A wave is a disturbance that transmits energy through a medium.

Wavelength, , is the distance between the tops of two successive crests (or the bottoms of two troughs). Frequency, , is the number of crests or troughs that pass through a given point per unit of time. The speed of light, c, is constant velocity of electromagnetic radiation, 2.997925 x 108 ms-1 in a vacuum, and the relationship between this speed and the frequency () and wavelength of electromagnetic radiation () is c = .

2.2 The Electromagnetic spectrum The visible spectrum: White light consists of a large number of light waves with different wavelengths. When a beam of white light is passed through a transparent medium, the wavelength components are refracted differently. The light is dispersed into a band or spectrum of colors. Atomic spectra: The spectra produced by certain gaseous substances consist of only a limited number of colored lines with dark spaces between them. These discontinuous spectra are called atomic or line spectra. Balmer's equation, for the wavelengths of atomic spectra lines of hydrogen, written in a form proposed by J. Rydberg, is = 3.2881 x 1015 s2.3 Quantum Theory Planck postulated that the energy of a quantum of electromagnetic radiation is proportional to the frequency of the radiationthe higher the frequency, the greater the energy. Planck's equation is E = h . The proportionality constant, h, called Planck's constant, has a value of 6.626 x 10-34 J s.
1 _ 1 n2 22
1

Example:2.1 For radiation of wavelength 242.4 nm, the longest wavelength that will bring about the photodissociation of O2, What is the energy of (a) one photon and (b) a mole of photons of this light? Solution: c = 2.998 x 108 m s-1 = 242.4 nm = 242.4 x 10-9 m (a) = = 242.4 x 10-9 m
c 2.998 x 108 m s-1

= 1.237 x 1015 s-1

E = h = 6.626 x 10-34 J s/photon x 1.237 x 1015 s-1 = 8.196 x 10-19 J/photon (b) E = 8.196 x 10-19 J/photon x 6.022 x 1023 photons/ mol = 4.936 x 105 J/ mol

2.4 Bohr's atomic model for a hydrogen atom 1. 2. The electron moves in circular orbits about the nucleus, with the motion described by classical physics. The electron has only a fixed set of allowed orbits, called stationary states. The allowed orbits are those in which certain properties of the electron have unique values.

3. An electron can pass only from one allowed orbit to another. In such transitions, fixed discrete quantities of energy (quanta) are involved, in accordance with Planck's equation, E = h. When the electron is attracted to the nucleus and confined to the orbit n, energy is emitted. The electron energy becomes negative, with its value lowered to En = -RH 2
n

RH is a numerical constant with a value of 2.179 x 10-18 J.

Example: 2.2 Is it likely that there is an energy level for the hydrogen atom, En = - 1.00 x 10-20 J? Solutoin: n2 = - RH / En
n2 -2.179 x 10-18 J = -1.00 x 10-20 J
2.179 x 1020 217.9

n = 14.76 Since the value of n is not an integer, this is not an allowed energy level for the hydrogen atom. Wave-Particle Duality According to de Broglie's hypothesis, the wavelength associated with a particle is related to the particle momentum, p, and Planck's constant, h. Momentum is the product of mass, m, and velocity, , = = h h Example: 2.3 p m What is the wavelength associatedwith electrons traveling at one-tenth the speed of light? Mass of an electron = 9.109 x 10-31 kg, = 3.00 x 107 m s-1 , h = 6.26 x 10-34 J s. Solution: m = 9.109 x 10-31 kg = 3.00 x 107 m s-1 h = 6.26 x 10-34 J s = 6.26 x 10-34 kg m2 1 = (9.109 x 10-31 kg) (3.00 x 107 m s-1) = 2.42 x 10-11 m = 24.2 pm Heisenberg uncertainty principle Heisenberg uncertainty principle is that we cannot measure position and momentum with great precision simultaneously. There must always be
6.26 x 10-34 kg m2 1

uncertainties in measurement such that the product of the uncertainty in position x, and the uncertainty in momentum, p, is x, p h
4

2.5

Quantum numbers and electron orbitals

Four sets of quantum numbers:

(i) Principal quantum number: The principal quantum number, n, have only a positive, nonzero integral value. n = 1, 2, 3, 4, ----(ii) Orbital (angular-momentum) quantum number: The orbital quantum number, l, may be zero or a positive integer, but not larger than n - 1 (where n is the principal quantum number). l = 0, 1, 2, 3, ------, n-1 (iii) Magnetic quantum number: It, ml, may be a negative or positive integer, including zero, and ranging from l to +1 (where l is the orbital quantum number). ml = -l, -l + 1, -l + 2, -----, 0, 1, 2, -----, + l (iv) Spin quantum number: The electron spin quantum number, ms, may have a value of + 1/2 ( also denoted by the arrow ) or 1/2 ( denoted by the arrow ) ; the value of ms does not depend on any of the other quantum numbers. Example: 2.4 Can an orbital have the quantum numbers n = 2, l = 2, ml = 2? Solution:

No, that is due to the followings. (1) The l quantum number cannot be greater than (n 1) . Thus, if n =2, l can only be 0 or 1. (2) If l can only be 0 or 1, ml cannot be 2; (3) Thus, if l =0, ml must be 0 and, if l = 1, ml may range from 1 to +1. Example: 2.5 Give the orbital designation specified by the quantum numbers. (a) n = 4, l = 0 Solution: (a) When l =0 the orbitals are s, so that is 4s orbital. ( b) When l =1 the orbitals are p, so that is 4s orbital.
Principal shells and Subshells

(b) n = 3, l = 1

(i) All orbitals with the same value of n are in the same principal electronic shell or principal level, and (ii) all orbitals with the same n and l values are in the same subshell or sublevel. Allowed values and orbital designations of quantum numbers. Princi pal Q.No (n) 1 Orbital Q.No ( l) (n-1) 0 0 1 Magnetic Q.No (ml) (2l+1) 0 0 +1, 0, -1 Orbital designation

1s 1s 2p 2p 2p

0 3 1 2

0 +1, 0, -1 +2,+1, 0, -1,-2

3s
3p 3p 3p

3d 3d 3d 3d 3d

Practice Example: 1. 2. For an orbital with n = 3 and ml = -1, what are the possible vales of l. Write an orbital designation corresponding to the quantum number n =4, l = 2, ml = 0.

2.6 Electron configuration The electron configuration of an atom is a designation of how electrons are distributed among various orbitals. Rules for assigning electrons to orbitals

( I ) Electrons occupy orbitals in way that minimizes the energy of the atom. The order in which orbitals fill is: 1s, 2s.2p, 3s.3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p ( ii ) No two electrons in an atom may have all four quantum number alike: Pauli exclusion principle: Only two electrons may exist in the same orbital and these electrons must have opposing spins. Because of this limit of two electrons per orbital, the n subshell consists of one orbital with a capacity of two electrons; the p subshell consists of three orbitals with a capacity of six electrons; and so on. ( iii ) When orbitals of identical energy are available, electrons initially occupy these orbitals singly.

Hund's rule: An atom tends to have as many unpaired electrons as possible.

The Aufbau Process:

Hypothetically the electron configurations of the atoms can be build up by placing electrons in the lowest available orbitals until the total number of electrons added is equal to the atomic number. Element:
1H

Electron confi: (spdf Notation) 1s1

Orbital diagram:
1s

2s
2 He

2s2
1s 2s 2p

6C

1s2, 2s2 2p2 Electron confi: (spdf Notation)

1s 2s 2p

Element:

Orbital diagram:

7N

1s2, 2s2 2p3

1s 2s 2p

8O

1s2, 2s2 2p4 Electron confi: (spdf Notation)

1s 2s 2p

Element:

Orbital diagram:

9F

1s2, 2s2 2s5

1s 2s 2p

10 Ne

1s2, 2s2 2s6

3s

11

Na

[Ne] 3s1

[Ne]

3s
18 Ar

3p

[Ne] 3s23p6 [Ar] 3d14s2 [Ar] 3d34s2 [Ar] 3d 4s

10 5 1

[Ne]
3d 4s

21

Sc V Cr

[Ar]
3d 4s

23

[Ar]
3d 4s

24

[Ar]
3d 4s
1

29 Cu

[Ar] 3d 4s [Ar] 3d 4s
10

[Ar]
3d 4s

30 Zn

[Ar]

Example 2.6: Using spdf Notation for an Electron Configuration. (a) Identify the element having the electron configuration. 1s2, 2s2 2s6, 3s23p5 (b) Write out the electron configuration of Arsenic. Solution: a. b. Superscript numerals (2 + 2 + 6 + 2 + 5) = atomic number 17; the element is chlorine. As (Z = 33): [Ar] 3d104s24p3

CHAPTER 3 3. The periodic table and some atomic properties

3.1 Modern periodic table Most modern periodic tables arrange the elements in 18 groups and the table can be divided into four blocks of elements, according to the subshells involved in the Aufbau process. s-block: Group 1A (alkali metals: ns1 electron configuration) and 2A (alkaline earth metals:ns2) as main group or representative elements . The group number = number of outermost s orbital e-s . p-block: Groups 3A, 4A, 5A, 6A, 7A: ns2 npx, and 8A: noble gases: ns2 np6 as representative elements. The group number = the sum of the ns and np electrons. d-block: Groups 3B, 4B, 5B, 6B, 7B, 8B, 1B, and 2B: transition elements :ns, (n-1) d e- configuration. The group number = the sum of the ns and (n-1) d electrons. Group number of 1B and 2B correspond to the number of outermost electrons. f-block: Inner transition elements: lanthanide and actinide series, having (n-2) f orbitals filled.
Main group element
1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr *Lanthanum series *Actinum series 58 Ce 90 Th 59 Pr 91 Pa 2A 4 Be 12 Mg 20 Ca 38 Sr 56 Ba 88 Ra 60 Nd 92 U d-block

p-block
3A 4A 5A 6A 7A 6 C 14 Si 32 Gr 50 Sn 82 Pb 7 N 15 P 33 As 51 Sb 83 Bi 8 O 16 S 34 Se 52 Te 84 Po 9 F 17 Cl 35 Br 53 I 85 At 2 He 10 Ne 18 Ar 36 Kr 54 Xe 86 Rn 5 B 8B 27 Co 45 Rh 77 Ir 109 67 Ho 99 Es 68 Er 100 Fm 69 Tm 101 Md 70 Yb 102 No 71 Lu 103 Lr 1B 2B 29 30 Cu Zn 47 Ag 79 Au 48 Cd 80 Hg 13 Al 31 Ga 49 In 81 Tl

Transition element
3B 21 Se 39 Y 57* La 89** Ac 61 Pm 93 Np 4B 22 Ti 40 Zr 72 Hf 104 62 Sm 94 Pu 5B 23 V 41 Nb 73 Ta 105 63 Eu 95 Am 6B 24 Cr 42 Mo 74 W 106 64 Gd 96 Cm 7B 25 Mn 43 Te 75 Re 107 65 Tb 97 Bk 26 Fe 44 Ru 76 Os 108 66 Dy 98 Cf 28 Ni 46 Pd 78 Pt

3.2 Atomic properties The sizes of atoms and ions:

Covalent radius: One half the distance between the nuclei of two identical atoms joined by a single covalent bond. Ionic radius: The distance between the nuclei of ions joined by an ionic bond. Metallic radius: One half the distance between the nuclei of two atoms in contact in the crystalline solid metal. Unit for atomic radius: 1 A0(angstrom) = 10-10 m SI units: 1 nm (nanometer) = 103pm (picometer) = 1x10-9m

Variation of atomic radii within a group: Down a group, atomic radius increases. Because the more electronic shells in an atom, the larger the atom will

be. Variation of atomic radii within a period: From left to right across a period, atomic radius decreases. As the effective nuclear charge (Zeff ) increase, the core and outer-shell electrons are attracted more strongly to the nucleus resulting in an overall contraction of the size of the atom. Variaton of atomic radii within a transition series: Atomic radii do not change very much within a transition series. Due to the fact that additional electrons go into an inner electron shell where they participate in shielding outer-shell electrons from the nucleus; at the same time, the number of electrons in the outer-shell tends to remain constant; thus the outer-shell electrons experience a roughly comparable force of attraction to the nucleus throughout a transition series. Ionic radius:

(i) Cations are smaller than the parent atoms.

Because there is an excess of nuclear charge over the number of electrons in the resulting cation when a metal atom loses one or more electrons to form a positive ion. For isoelectronic cation, the more positive the ionic charge is, the smaller is the ionic radius. (ii) Anions are larger than the parent atoms. Due to the following facts. 1. When a nonmetal atom gains one or more electrons to form an anion, the nuclear charge remains constant, but Zeff is reduced because of the additional electron (s), so the electrons are not held as tightly. 2. Repulsion among electrons increase.

Example 3.1: Determine which is the largest atom: Sc, Ba, Se. Solution: [Ar] 4s23d1 [Xe] 6s2 56Ba: 2 10 4 34Se: [Ar] 4s 3d , 4p
21Sc:

(Period:4, Group:3B) (Period:6, Group:2A) (Period:4, Group:6A)

In the same period 4, Sc is closer to the left than Se; Sc < Se Zeff : Atomic size: Sc > Se Ba is in the sixth period and so has more electronic shells than either Sc or Se, Ba atom is the largest of the three.

Example 3.2: Compare the ionic sizes in each of the following pairs. a. K+, Ca2+ b. Cl-, S2Solution: a. K+ : [Ne] 3s23p6

Ca2+: [Ne] 3s23p6 Both are isoelectronic cations; for isoelectronic cations, the higher the charge is, the smaller is the ion and thus, Ca2+ is smaller than K+ion. b. [Ne] 3s23p6 Cl- : S2- : [Ne] 3s23p6 Both are isoelectronic anions; for isoelectronic anions, the higher the charge is, the larger the ion and so, S2- is larger than Cl- ion.

Example 3.3: Arrange the following species in order of increasing size: Ar, K+, Cl-, S2-, Ca2+ Solution: 1. 2. 3. 4. 5. The five species are isoelectronic , having the electron configuration of Ar: 1s2 ,2s22p6 ,3s23p6 . For isoelectronic cations, the higher the charge is, the smaller is the ion. Thus, Cationic size: Ca2+ < K+ Because K+ has the higher nuclear charge than Ar, size: K+ < Ar Because Ar has higher nuclear charge than Cl--, size: Ar < ClFor isoelectronic anions, the higher the charge is, the larger is the ion. Thus, anionic size: Cl- < S2 The order of increasing size is Ca2+ < K+ < Ar < Cl- < S2

Ionization energy The ionization energy, I, is the quantity of energy a gaseous atom must absorb so that an electron is stripped from the neutral atom. Mg (g) Mg +(g) + e-

First ionization energy: the energy required to strip one electron from a neutral gaseous atom. Second ionization energy: the energy required to strip one electron from a gaseous ion with a charge of +1. Second ion energy: I2 is larger than the first I1: Mg (g) Mg+ (g)
I1 I2

Mg +(g) + eMg+2 (g) + e-

This is due to the fact that the attraction between the positive ion and the electron is stronger than between the neutral atom and the electron. Variation of ionization energy within a group: Down a group, ionization energy decreases as atomic radii increases. Because the farther an electron is from the nucleus, the more easily it can be extracted. Variation of ionization energy within a period: From left to right across a period, ionization energy increase as atomic radii decreases. Because the larger effective nuclear charge makes removal of the electron more difficult.

Example 3.4: Predict which member of each pair has the higher ionization energy. a. Al or Mg b. P of S Solution: a. : [Ne] 3s2 (Period.3, Group.2A) 2 1 (Period.3, Group.3A) 13Al : [Ne] 3s 3p More energy is required to strip an electron from the lower energy 3s orbital in Mg than from the 3p orbital in Al. Ionization energy: Mg > Al. [exception]
12Mg

3s

3p

b.

15P 16S

: :

[Ne]
3s 3p

(Period.3, Group.5A) (Period.3, Group.6A)

[Ne]

I1 for S is slightly lower than for P because repulsion between the pair of electrons in the filled 3p orbital of an S atom makes it easier to remove one of those electrons than an unpaired electron from a half-filled 3p orbital of a P atom. [exception] Electron affinity Electron affinity, EA, is a measure of the energy change that occurs when a gaseous atom gains an electron. F(g) + eF-(g) EA = -322.2 kJ/mol

When an F atom gains an electron, energy is given off. The process is exothermic, the electron affinity is a negative quantity. For some atoms the gain of an electron required that energy be absorbed. The process is endothermic, and the EA has a positive value. This is the case for the noble gases, where the added electron enters the empty s orbital of the next electronic shell. Ne (g) + e(1s22s22p6) Ne-(g) EA = + 29 kJ/mol

(1s22s22p6, 3s1)

For an element such as oxygen EA1 is negative and EA2 is positive. When the second electron added is approaching a negative ion, a srong repulsion is felt and the energy of the system increase. O (g) O-(g) + e+ eO -(g) O2- (g) EA1 = -141.4 kJ/mol EA2 =+141.4 kJ/mol

Magnetic properties

A diamagnetc atom or ion has paired electrons, and these individual magnetic effects cancel out. A diamagnetic species is weakly repelled by a magnetic field. For example,
3s
12

Mg [Ne] 3s

[Ne]

Magnesium is diamagnetic, corresponding to two 3s electrons. They must be paired , as are all the other electrons. A paramagnetic atom or ion has unpaired electrons, and the individual magnetic effects do not cancel out. The unpaired electrons induce a magnetic field that causes the atom or ion to be attracted into an external magnetic field. The more unpaired electrons present, the stronger the attraction. For example,

3s
11

Na [Ne] 3s1

[Ne]

Sodium is diamagnetic, corresponding to a single 3s unpaired electron outside the Ne core. 3.3 Other period properties of the elements Physical properties of the elements Variation within a group The value of a property often changes uniformly down a group for compounds as well as for elements . To explain this trend, it is needed for the relationship between melting point and intermolecular forces of attraction: the stronger these forces, the higher the melting point. And in general, the higher the molecular mass, the stronger the intermolecular forces in a substances. Variation within a period A few properties vary regularly across a period in general. The ability to conduct heat and the ability to conduct electricity are two that do. Thus among the third period elements, Na, Mg, Al have good thermal and electrical conductivity. The nonmetals P, S, Cl, and Ar have poor thermal and electrical conductivities. Chemical properties of the elements Some variations within groups of elements and some variations across a period will be considered as follows. Reducing abilities of group 1A and 2A metals

The lower the ionization energy, the better the metal is as a reducing agent and the more vigorous its reaction with water. The reducing agent makes possibly a reduction half-reaction and itself, by losing electrons, is oxidized. Indeed, reducing ability depends on the ionization energy. In-group 1A metals, K, for instance, have lower ionization energy than does the next number of the fourth period, Ca. The expectation is that K reacts more vigorously with water than does Ca. 2K (s) + 2 H2O Ca (s) + 2 H2O 2 K+(aq) + 2 OH-(aq) + H2 (g) Ca2+(aq) + 2 OH-(aq) + H2 (g)

With respect to group 2A, Mg and Be do not react with cold water as do the other alkaline earth metals. This is on account of their higher ionization energies compared with the other group 2A metals.

Oxidizing abilities of the halogen elements The higher the electron affinity, the better the nonmetal is as an oxidizing agent.

An oxidizing agent makes possibly an oxidation half reaction and itself, by gaining electrons, is reduced. Hence, electron affinity is related to the gain of electrons. We might expect an atom with a strong tendency to gain electrons (a large negative electron affinity) to take electrons away from atoms that lose electrons without much difficulty (low ionization energies). (i) In these term, it is understandable that active metals (group1A) form ionic compounds with active nonmetals (group 7A). 2 Na (s) + Cl2 (g) 2 NaCl (s) (ii) In displacement reaction, two halogens, one in molecular form and the other in ionic form, exchange places. Cl2(g) + 2I -(aq) I2(aq) + 2 Cl-(aq)

Acid-base nature of element oxides

(i) Some metal oxides, such as Li2O, react with water to produce basic metal hydroxides, called basic oxides. Li2O (s) + H2O 2 Li -(aq) + 2 OH-(aq) (ii) Some nonmetal oxides, like CO2 (g) , produce acidic solutions in water. These nonmetal oxides are acidic oxides. CO2 (g) + H2O H2CO3 (aq)
(iii) It should be expected that the metal oxides at the left of the period to be basic and the nonmetal oxides at the right to be acidic.

CHAPTER. 4 4. Chemical reactions and Stoichiometric Calculation

4.1 Chemical reactions

A chemical reaction is a process in which one set of substances called reactants is converted to a new set of substances called products. Sometimes products reacts to reform the original reactants that is called reversible reactions. For example, decomposition of silver oxide is illustrated as follow. 2 Ag2O(s)
_4

Ag ( s) + O2 (g)

stoichiometric coefficients Reaction conditions: Temperature, pressure, and catalyst State of matter: (s) = solid; (l) = liquid; (g) = gas; (aq) = aqueous (water) solution

4.2 Stoichiometry
It means the quantitative (mole) relationships among the reactants and products in a reaction. N2 (g) + O2 (g) Stoichiometry: 1 mole 1 mole 2 NO(g) 2 moles

Avagadro's constant: 6.02x1023 atoms /molecule For an element, 1 mole of an element contains 6.02x1023 atoms. For a compound, 1 mole of compound contains 6.02x1023 molecules.

Stoichiometric calculations: Reactant (A) mass of substance A

1

Product (B)
2

mole of substance A

mole of substance B

mass of substance B

*molar mass: (1), (3) ; *stoichiometric factor: (2) 1 molar mass. = 40g NaOH = 1 mole. NaOH = 6.02x1023 molecules. 1molar mass = 108 g Ag = 1 mol of Ag = 6.02x1023 atoms. N2 (g) + 3 H2 (g) 2 NH3(g)

1 mole of N2 produces 2 moles of NH3 . 3 mole of H2 produce 2 moles of NH3 .

Hence, stoichiometric factor based on N2 and H2 are 2 and 2/3 respectively. 4.3 Chemical reactions in solutions: Solute + solvent solution

The solvent is the component that is present in the greatest quantity in a solution and the solute is less quantity. The solution is a homogeneous mixture of solvent and solute. Molarity: Molarity =
Amount of solutes (moles)
Volume of solution (liters)

Unit: mol /L n = C.V

Concentration:

C =

n (mol) V (liters)

Solution dilution: When a solution is diluted, the amount of solute remains constant between the initial (i) and final (f) solution.

ni = n f Ci Vi = Cf Vf

1.4 Determining the limiting reagent Limiting reagent: The reagent or reactant that is completely consumed in a reaction is known as limiting reagent or limiting reactant. The quantity of products formed depends on the quantity of limiting reagent. For example, Stoic. Ratio: (Relationship) Reactants: 2 H2 (g) 2 mol [10mol] + O2 (g) + 1mol [7mol] 2 H2O(g) 2 mol

Assuming that H2 is the limiting reagent: Required mol of O2 = 10 mol H2 x

1mol O2
2 mol H2

= 5 mol O2

[7 mol present 5 mol consumed = 2 mol O2 in excess] O2 is in excess; so H2 is the limiting reagent. Theoretical Yield The calculated quantity of product in a chemical reaction is called theoretical yield of a reaction. Actual Yield The quantity of product that is actually produced is called the actual yield. Percent Yield Percent Yield = Actual yield Theoretical yield x 100 %

Consecutive reaction Reaction that are carried out one after another in sequence to yield a final product are called consecutive reaction . For example : 2 S (s) + 3 O2 (g) SO3 (g) + H2O (l) 2 SO3 (g) H2SO4 (l)

Simultaneous reaction In simultaneous reaction, two or more substances react independently of each other in separate reactions occurring at the same time. For example: Mg(s) + 2 HCl(aq) Zn(s) + 2 HCl(aq) Mg Cl2 (aq) + H2 (g) Zn Cl2 (aq) + H2 (g)

4.5 Introduction to Reactions in Aqueous solutions. Solute

+ Nonelectrolyte Strong electrolyte Weak electrolyte Water itself is nonconductor Conductor or nonconductor

Solvent Solution

Characteristic classification of the solute. Nonelectrolyte Strong electrolyte A nonelectrolyte is a substance that is not ionized and does not conduct electric current. A strong electrolyte is completely ionized in water solution and the solution is a good conductor. HCl (aq) H+ (aq) + Cl- (aq)

Weak electrolyte

A weak electrolyte is partially ionized in water solution and the solution is only a fair conductor of electricity. HC2H3O2 (aq) H+(aq) + C2H3O2- (aq) (CH3COOH)

4.6

Predicting Precipitation Reactions

A Set of Solubility Rules:

Soluble salts Group IA metal salts NH4+ salts NO3- Salts

Insoluble salts (precipitate) CO32-, OH- and, S2- Salts Chlorides, bromides and, iodides of Pb2+,

Cl-, Br-and, I- Salts SO42- salts

Ag+ and, Hg2+2 Sulfates of Sr2+, Ba2+, Pb2+ and, Hg2+2

Hydroxides and sulfides . of Ca2+, Sr2+, Ba2+are slightly Soluble

Molecular equation: Mg (OH)2 (s) + 2 HCl (aq) Net ionic equation: Mg (OH)2 (s) + H+ (aq) Mg2+(aq) + 2 H2O(l) Mg Cl2 (aq) + 2 H2O (l)

4.7 Acid-Base Reaction An acid: A substance that provides hydrogen ions (H+) in solution. (Hydronium ion, H3O+) aqueous

Strong Completely ionized in aqueous solutions, such as, acids HCl, HBr, HI, HCLO4, HNO3, and H2SO4. H+(aq) + NO3-(aq) HNO3(aq)

Partially ionized in aqueous solutions; the Weak ionization is reversible, eg., HCOOH, CH3COOH acids H+(aq) + C2H3O2- (aq) HC2H3O2 (aq)

A Base : A base is a substance capable of providing hydroxide ions (OH-) in aqueous solution.

Strong Completely ionized in aqueous solutions, i.e., bases Hydroxides of Gp.IA and some Gp.IIA metals. NaOH(aq) Na+(aq) + OH -(aq)

Partially ionized in aqueous solutions; the Weak ionization is reversible, e.g., NH3, NH4+ bases NH4+(aq) + OH- (aq) NH3(aq) + H2O

Neutralization: In a neutralization reaction, an acid and a base react to form water and aqueous solution of an ionic compound called a salt. HCl(aq) + NaOH(aq) Na Cl(aq) + H2O(l)

4.8 Oxidation-Reduction Reaction: Oxidation: Oxidation is a process in which the oxidation state of element increases.

 Reduction: Reduction is a process in which the oxidation state of element decreases.

Balancing oxidation-reduction reaction: (Half-reaction method)

Balancing the equation for a redox reaction in acid solution is as follow. SO32-(aq)+ MnO4-(aq)+ H+ 1. SO32-(aq) MnO4-(aq) 2. SO32-(aq) + H2O MnO4-(aq) SO32-(aq) + H2O MnO4-(aq) + 8 H+(aq) SO42-(aq) + Mn2+(aq) + H2O(aq) SO42-(aq) Mn2+(aq) SO42-(aq) Mn2+(aq) + 4H2O SO42-(aq) + 2 H+(aq) Mn2+(aq) + 4H2O

3. SO32-(aq) + H2O SO42-(aq) + 2 H+(aq) + 2 eMnO4-(aq) + 8 H+(aq) + 5 eMn2+(aq) + 4H2O 4. 5 SO32-(aq)+ 5 H2O 5 SO42-(aq)+ 10 H+(aq)+ 10 e2MnO4-(aq)+ 16H+(aq)+ 10 e2Mn2+(aq) + 8H2O 5 SO32-(aq)+ 2MnO4-(aq)+ 6H+(aq) 5 SO42-(aq)+ 2Mn2+(aq) + 3H2O 5.
Verify: net charge (-6)

net charge (-6)

Practice Example:

Balance the following equations for the redox reactions. 1. SO32-(aq)+ Cr2O72-(aq)+ H+(aq) 2. CrO42-(aq)+S2-(aq)+OH-(aq) 3. S2O32-(aq) + H+(aq) 4. H2O2 (aq) + Fe2+(aq)+ H+(aq) SO42-(aq)+Cr3+(aq)+H2O Cr(OH)3(s)+ S (s) + H2O S(s) + SO2 (g) + H2O H2O + Fe3+(aq)

4.9

Disproportionation Reaction:

Some oxidation-reduction reactions, in which the same substance is both oxidized and reduced, are called disproportionation reactions.
red: oxi: 0 -2

-1

2H 2 O 2 (aq)

2H 2 O + O 2 (g)

4.10 Oxidizing and Reducing Agents: Oxidizing agent; oxidant: The substance that causes some other substance to be oxidized and so itself reduced. Reducing agent; reductant: The substance that causes some other substance to be reduced and so itself oxidized. 2 Na (s) + Cl2 (g) red. agent oxi. agent For the above reaction, Na makes Cl2 to be reduced to Cl- in NaCl and itself oxidized to Na+in NaCl; Na is reducing agent. Cl2 makes Na to be oxidized to Na+ in NaCl and itself reduced to Cl-in NaCl; Cl2 is oxidizing agent. 4.11 Stoichiometric Calculations in Aqueous Solutions 2 NaCl (s)

Example: Vinegar is a dilute aqueous solution of acetic acid. A 5 ml sample of a particular vinegar was titrated with 38.08 ml of 0.1 M NaOH (aq). The legal minimum A/A content of vinegar is 4% by mass.

(i) Determine the concentration of HC2H3O2. (ii) Does this sample exceed the minimum limit? (Density of vinegar = 1.01 g/mL) Solution: HC2H3O2(aq)+ OH-(aq) (i) ml NaOH L NaOH C2H3O2-(aq)+ H2O(l) mol NaOH conc.HC2H3O2
1L 0.1mol NaOH 1L 1mol OH1mol NaOH

mol OH-

mol HC2H3O2

mol OH = 38.08 ml x

1000 ml

= 3.808 x 10-3 mol OHmol HC2H3O2 = mol OH- = 3.808 x 10-3 mol HC2H3O2 Conc.HC2H3O2 =
3.808x10-3mol HC2H3O2 5.00x10 L
-3

= 0.762 M C2H3O2 60.05 gHC2H3O2 1 mol HC2H3O2

(ii) % HC2H3O2 =

0.762mol HC2H3O2 1000 ml vinegar

1.01 g i = 4.53 % HC2H3O2

1 ml vinegar

x 100 %

The vinegar sample does exceed the legal minimum limit. Practice Example: A 0.235 g sample of a solid that is 92.5% KOH, 7.5% Ba (OH)2 by mass requires 45.62 ml of an HCl (aq) solution for its titration. What is the molarity of the HCl (aq)? (Hint: Write a net ionic equation, and there are two sources of OH-)

CHAPTER 5. 5. The properties of gases

5.1 The concept of pressure Pressure is defined as a force per unit area. A force divided by the area over which the force is distributed
F P= A

SI unit: N/m2 (Pascal: 1P a = 1 N/m2)

Kilopascal: kPa is more commonly used

Liquid pressure The pressure of a liquid depends only on the height of column and the density of the liquid.
P= F W g.m g.V.d g.h.A.d = = = = = g.h.d A A A A A

g = Acceleration due togravity:9.80665 m s-2 h = Height of liquid; d = density of liquid. Barometric pressure To measure the atomospheric pressure, barometer is used. The height of mercury in a barometer,called the barometric pressure, varies with atmospheric conditions and with altitude. The pressure exerted by a mercury column of exactly 760mm in height is called the standard atmosphere (atm). 1 atm = 760 mmHg; 1 atm = 760 torr (Torricelli).

Example: 5.1 What is the height of a column of water that exerts the same pressure as a column of mercury 76.0 cm (760mm) high?

Solution: Pressure of Hg column = ghHg dHg = g x 76.0 cm x 13.6g/cm3 Pressure of H2O column = g h H O d H O = g x h H O x 1.00 g / cm 3
2 2 2

g x h H 2O x 1.00 g / cm 3 = g x 76.0 cm x 13.6 g / cm 3

h H 2O 13.6 g / cm 3 = 76.0 cm x = 1.03 x 10 3 cm = 10.3 m 3 1.00 g / cm

We see that the column height is inversely proportional to the liquid density: for a given liquid pressure, the lower the liquid density is the greater is the height of the liquid column. Manometers One can compare the gas pressure and barometric pressure with a manometer. As long as the gas pressure being measured and the prevailing atmospheric (barometric) pressure are equal, the heights of the Hg column in the two arms of the manometer are equal. A different in height of the two arms signifies a difference between the gas pressure and barometric pressure. 1. If Pgas>Pbar ; P = positive value. 2. If Pgas < Pbar ; P = negative value. Example: 5.2 What is the gas pressure Pgas, if the conditions, gas pressure less than barometric pressure, are these: the manometer is filled with liquid mercury (d = 131.6 g/cm3); barometric pressure is 748.2 mmHg; and the difference in mercury levels is 8.6 mmHg? Solution: Whether the situation corresponds to gas pressure less than barometric pressure, the pressure we seek is Pgas = Pbar + P. As the gas pressure is less than barometric pressure; P is negative, Pgas = Pbar - P = 748.2 mmHg 8.6 mmHg = 739.6 mmHg.

5.2 The simple gas law Boyles Law For a fixed amount of gas at a constant temperature, gas volume is inversely proportional to gas pressure.
1 or V P1V1 = P2 V2 P PV = a (cons tant )

Example: 5.3 The tank is first evacuated, and then it is connected to a 50.0-L cylinder of compressed nitrogen gas. The gas pressure in the cylinder, originally at 21.5 atm, falls to 1.55 atm after it is connected to the evacuated tank. What is the volume of the tank? Solution:
P1V1 = P2 V2

V2 = V1 x

P1 215 atm = 50.0 L x = 694 L P2 1.5 atm

Of this volume, 50.5 L is that of the cylinder. The volume of the tank is 694 L 50.0 L = 644 L. Charles Law The volume of the fixed amount of gas at constant pressureis directly proportional to the Kelvin (absolute) temperature. V T or V = bT (where b is constant) Relationship: T (K) = t (C) + 273.15 STP condition: 0C = 273.15 K and 1 atm = 760 mmHg Avogadros Law At a fixed temperature and pressure, the volume of the gas is directly proportional to the amount of gas.

Molar volume: 1 mol of gas = 22.4 L at STP = 6.023 x 1023molecules Example: 5.4 1. 2. What is the mass of 1 L cyclopropane C3H6 at STP? 128 g pieces of solid CO2 (s) sublimates into CO2 (g) . What is the volume of this gas at STP in Liters?

Solution: 1. 2. (?) g C3H8 = (?) L CO2 =

1 mol 42g x = 1.875 g 1 mol 22.4 L 22.4L 1 mol x x 128 g = 65.1636 L CO 2 1 mol 44g

The Ideal gas equation From the gas law relationships,

V nT P

and

V=R

nT P

PV = nRT ; R = Ideal gas constant Example: 5.5 What is the volume occupied by 13.7 g Cl2(g) at 45C and 745 mmHg. Molar mass of Cl2 = 71 g/mol Solution: (?) n of Cl2 = P=
1mol x 13.7 g = 0.193 mole 71g

1 atm 760 mmHg

x 745 mmHg = 0.9803 atm

T = 45C + 273.318 K PV = nRT

V=

nRT 0.193 mole x 0.08205 L atm / mol.K x 318 K = P 0.980263 atm

= 5.1364 L. Example: 5.6 5.6An oxygen gas is filled into 1L flask at STP. Suppose that. the pressure remains at 1 atm, when the O2 (g) is heated to 100C, what mass of O2 must release from the flask? Solution:

1mole At STP, (?) mole O2 = 22.4 L x 1L = 0.04464 mole At 100C, (?) mole O2,

PV = nRT

or

R=

P1V1 PV = 2 2 n 1T1 n 2 T2

PV nT

n1T1 = n2 T2

(as P, V remains constant) T2 = 100C + 273 = 373 K

T1 = 0C + 273 = 273 K, and n2 =

0.0446 mole x 273K 373 K = 0.0364 mole O2 (in flask)

Thus, Released O2 (mole) = 0.0446 0.03264 = 0.012 mole Molar mass of O2 = 32 g/mole, 32 g x 0.012 mole = 0.384 g O2 (g) O2 released = 1 mole

5.3 Applications of the ideal gas equation Molar mass determination

Since the number of moles of gas (n) is equal to the mass of gas (m) divided by the molar mass (M), that is n = m/M, substituting into the ideal gas equation.
PV = mRT M

Gas density To determine the density of gas, d,

nxM n = xM V V m MP d= V = RT

d= V=

Example: 5.7 What is the density of oxygen gas at 298K and 0.987 atm? Solution: d=
m MP 32.00 g / mol x 0.987 atm = = 0.08206 Latm / mol.K x 298 K V RT

= 1.29 g / L

Example: 5.8

Gases in chemical reactions

What volume of N2(g) , measured at 735 mmHg and 26C, is produced when 70.0 g NaN3 is decomposed? 2NaN3(g)

2 Na(1) + 3 Na2(g)

Solution:

2NaN3(g) ? mol N2 =

2 Na(1) + 3 Na2(g)

= 1.62 mol N2 P = 735 mmHg x 1atm/760 mmHg = 0.967 mmHg V=? n =1.62 mol
R= 0.08206 L atm/mol.K

T = 26OC + 273 = 299 K ..-::P = 1.62 mol x 0.08206 Lmol-1K-1 x 299K 0.967 atm. = 41.1L Law of combining volume

Example:5.9

Zinc blend, ZnS, is the most important zinc ore. Roasting (strong heating) of ZnS is the first in the commercial production of zinc. 2ZnS(s) + 3 O2(g)

2ZnO(s) + 2S02(g)

What volume of SO(g) forms per liter of O2(g) consumed? Both gases are measured at 25 oC and 745 mmHg. 2ZnS(s) + 3 O2(g)

2ZnO(s) + 2S02(g) = 0.667 L S02

? L S02(g) = 1.00 L O2(g) x

Mixture of gaes

For the nonreactive gases, n = the total amount, in

moles, of the gaseous mixture (n tot) .Example: 5.10

What is the pressure exerted by a mixture of 1.0 g H2 and 5,00 g He when the mixture is confined to a volume of 5.0L at 20C? Solution: n.tot = 1.0 g H2 x = 0.50 mol H2 + 1.25 mol He = 1.75 mol mol gas P = nRT/V = 1.75molx0.08206Lmol-1K-1x293K = 8.4 atm 5.0 L

Daltns Law of partial pressures the partial pressures of the components of the mixture, * Ptot = PA + PB + ----In case of the wet gas collected over water, *Ttot = Tbar = Pgas + H2O For the composition of gaseous mixtures in % by volume, * Vtot = VA + VB + - (Vtot = total vol.of the gas)

The total pressure of a mixture of gases is the sum of

The mole fraction The mole fraction of a component. nA /n tot , in a mixture is the fraction of all molecules in the mixture contributed by that component.

n A PA VA = = n B PB VB
Example: 5.11
What are the partial pressure of Hz and He in the gaseous mixture described in example 5.10?

Solution:

From example 5.10, Ptot = 8.4 atm and so,

PH =
2

x Ptot = 0.50 mol x 8.4 atm = 2.4 atm

1.75 mol

PHe =

x Ptot = 1.20 mol x 8.4 atm = 6 atm

1.75 mol
Example: 5.12

Collecting a gas over a liquid (water).

In the following reaction 81.2 ml of O2(g) is collected over water at 23C and barometric pressure 7.51 mmHg. What must have been the mass of Ag2O(s) decomposed?

(Vapor pressure of water at 23C -= 21.1 mmHg.) 2A2O(s)

Solution:

4Ag(s) + O2(g)

1.

= 751 mmHg 21.1 mmHg = 750 mmHg = (750/760) atm = 0.961 atm V = 81.2 ml = 0.0812 L R = 0.08206 Latm-1K-1 T = 23oC + 273 = 293 K n=?

= 0.0082 mol n = PV/RT = 0.961 atm x 0.0812 L -1 1 0.08206 L atm mol K x 296K
2Ag2O(s) Ag2O(s) = 0.00321mol O2 x 4Ag(s) + O2(g) 2 mol Ag 2 O 231.7g Ag 2 O x = 1.49g Ag2O 1mol O 2 1 mol Ag 2 O

5.4 Kinecic molecular theory of gases 1.

A gas is composed of a very large number of extremely small particles (molecules or. in some cases, atoms) m constant, random, straight-line motion. Great distances separate molecules of a gas. The gas is mostly empty space. (The molecules are treated as if they have mass but no volume, so called "point masses.") . Molecules colloid with one another and with the walls of their container. However, these collisions occur very rapidly and most of the time molecules are not colliding. There are assumed to be no forces between molecules except very briefly during collisions. That is, each molecule acts independently of all the others and is unaffectedly by their presence. Individual molecules may gain otiose energy as a result of collisions. In a collection of molecules at constant temperature, however, the total energy remains constant. This theory depends on the following facts. (i)
The frequency of molecular collisions: The number of collision per second

2.

3.

4.

5.

The higher this frequency, the greater the total force of these collisions. Collision frequency increases with the number of molecules per unit volume and with molecular speeds.

(ii) The amount of translational kinetic energy: That is energy possessed by objects moving through space, represented as ek and has the value
eK = 1/2 mu2 m = the mass of the molecule and u = speed of the molecules

The faster molecules move, the greater are their translational kinetic energies and the greater is the force
of their collisions.

(iii) Molecules move in all direction and at different speeds:

When all factors are properly considered, the result

is this expression for the pressure of gas. The basic equation of the kinetic-molecular theory.
P=

1N mu 2 3V

N = the number of molecules present in the Volume V. m = mass of the molecules u2 = the average of the .squares of their speeds

Distribution of Molecular speed Root-mean-square speed, ursm thee square root of the average of the squares of the speeds of all the molecules in a sample.

Urms =

3RT M

(or) R = Gas constant, 8.3145 J mol-1 K-1 2 -2 -1 8.3145 Kg m s mol K-1

Example: 5.13

Which is The greater speed, that of a bullet from a high powered M-16 rifle (21~0 mi/h) or the root-mean-square speed of Hs molecules at 25C?
Solution:

3RT M R = Gas constant, 8.3145 J mol-1 K-1 MH2 = 2.016 x 10-3' kg mol-1 Urms =

Urms =

3 x 8.3145k gm 2 s -2 mol-1 K -1 x 298 K 2.016x10-3 Kg mol-l

= 4.29 x 103 mi/h Comparing the two speeds, the root-mean-square speed of H2 molecules at 25C is greater than the speed of the high-powered rifle bullet.
5.5 Gas properties relating to the kinetic-molecular theory

Diffusion: is the migration of molecules of different substances as a result of random molecular motion. Effusion: is the escape of gas molecules from their container through a tiny orifice or pinhole. The rates at which 'diffusion and effusion occur are directly proportional to molecular speeds. That is, molecules with high speeds diffuse and effuse faster than molecules with low speeds. Grahm 'a law

The rates of effusion (or diffusion) of two different gases are inversely proportional to the square root of their molar masses.

The result shown in the following equation is a kinetic-theorv statement of Graham's law.
3RT/M A MA rate of efusion of A (u rms ) A = = = rate of effusion of B (u rms ) B 3RT/M B MB A ratio of effusion-rates, times, distances, .... is equal to the square root of a. ratio of molar masses. 1. molecular speeds 2. rates of effusion Ratio of 3. effusion times = ratio of two molar masses 4 .distance traveled by molecules 5. amount of gas effused Example: 5.14

A sample of Kr(g) escape through a tiny hole in 87.3 s, and unknown gas requires 42.9 s under identical conditions. What is the molar mass of the unknown gas?
Solution: Again start with qualitative reasoning. Because the unknown gas effuses faster, it. must have a smaller molar mass than Kr. The ratio of molar masses in the setup below must be smaller than 1: Munk goes in the numerator.

efusion time for unknown 42.9 s M unk = = = 0.491 efusion time for Kr 87.3 s M Kr Munk = (0.491)2 x MKr = (0.491)2 x 83.80 = 20.2 g/mol
5.5 Nonideal (real) gases

Figure 5.1 The behavior of real gas compressibility factor as a function of pressure for three different gases at OoC.

All gases behave ideally at sufficiently low pressures, say, below I atm, but that deviations set in at increased pressures. At very high pressures the compressibility factor is always greater than 1. Here is how we might explain nonideal gas behavior: Boyle's law predicts that at very high pressures a gas volume becomes extremely small and approaches zero. This cannot be, however, because the molecules themselves occupy space and are practically incompressible. The PV product is larger than predicted for an ideal gas and the compressibility factor is greater than 1. We must also allow for the fact that mterrnolecular force exists in gases.
Figure 5.2 Intermolecular attraction.

forces of

Figure 5.2 suggests that because of attractive forces among the molecules, the forces of the collisions of gas molecules with. the container walls is less than expected for an ideal gas. Intermolecular forces of attraction account for compressibility factors less than 1. These forces become increasingly important at low temperatures, where molecular motion slows down. To summarize

o Gases tend to behave ideally at high temperatures and low pressures. o Gases tend to behave nonideally at low temperatures and high pressures.

The van der Waals equation

[ P + (n2 a)/V2 ] (V n b) = n RT V = the volume of n moles of gas. (n2a) /V2 is related to intermolecular .forces of attraction. It is added to P because the measured pressure is lower than expected (recall Figure5.2) b = the excluded volume per mole; related to the volume of the gas molecules.

(V n b) = free volume within the gas 'a', "b" = specific value for particular gas. varying with temperature and pressure.
Example: 5.13
Use the van der Waal's equation to calculate the pressure exerted by 1.00 mol C12(g) when it is confined to a volume of 2.00 L at 273 K.

(a = 6.49 L2 atm mol-2 b = 0.0562 L mol--1).

Solusion:

Solve van der Waal"s equation for P.

P=

n RT n 2a 2 V-nb V

n = I mol V = 2 mol T = 273 K R = 0.08206 L atm mol-1K-1 n2a = (I mol)2 x 6.49 L2 atm mol-1 = 6.49 L2 atm n b = 1 mol x 0.0562 L mol-1 = 0.0562 L mol-1 P = Imol x 0.08206 L atm mol-1K -1 6.49 L2 atm (2 0.0562)L 22 xL2

P = 11.5 atm -1.62 atm = 9.9 atm

CHAPTER 6 6. The preoperties of lquids and solids

6.1 Intermolecular forces and some properties of liquids

Surface tension

Surface tension, , is the energy or work required to increase the surface area of a liquid. It has the units of energy per unit area, typically J/m2.

As the temperatureand hence the intensity of molecular motion increases, intermolecular forces become less effective. Less work is required to extend the surface of a liquid, meaning that surface tension decreases with the increased temperature. When a drop of liquid spreads into a film across a surface, we say that the liquid wets the surface. Whether a drop of liquid wets a surface or retains its spherical shape and stand on the surface depends on the strengths of two types of intermolecular forces.
Cohesive forces are the intermolecular forces between like molecules, such as within a drop of liquid. Adheive forces are the intermolecular forces between unlike molecules, molecules of a liquid and of the surface with which it is in contact.

If cohesive forces are strong compared to adhesive forces, a drop maintains its shape. If adhesive forces are enough, on the other hand, the energy requirement for spreading the drop into a film is met through the work done by the collapsing drop. If the liquid in the tube is water, the interface between the water and the air above it, called a meniscus, is curved upward (concave). Water is drawn slightly up the walls by adhesive forces between water and the glass. With liquid mercury the meniscus is curved downward (convex). Cohesive forces in mercury, consisting of metallic bonds between Hg atoms, are strong; mercury does not wet glass.

The effect of meniscus formation is greatly magnified in tubes of small diameter, called capillary tubes. In the capillary action the water level inside the capillary is noticeably higher than outside.
Viscosity

Viscosity refers to a liquids resistance to flow. Its magnitude depends on intermolecular forces of attraction and, in some cases, on molecular sizes and shapes. The stronger the intermolecular forces of attraction are, the greater is the viscosity.

When a liquid flows, one portion of the liquid moves with respect to neighboring portions. Cohesive forces within the liquid create an internal friction which reduce the rate of flow. The effect is weak in liquid of low viscosity such as ethyl alcohol and water. They flow easily. Liquid such as honey and heavy motor oil flow much more sluggishly. We say that they are viscous.
Vaporization of liquid

The passage of molecules from the surface of a liquid into the gaseous or vapor state is called vaporization; the term evaporation also used.

The tendency for a liquid to evaporate increases with increased temperature and decreased strength of intermolecular forces.

Enthalpy of vaporization:

The enthalpy of vaporization is the quantity of heat that must be absorbed if a certain quantity of liquid is vaporized at a constant temperature.
H vaporization = H vapor H liquid

Vaporization is an endothermic process, H vap is always positive. In this text enthalpies of vaporization are expressed in terms of one mole of liquid vaporized.

Example: 6.1

To vaporize 1.75 g of acetone, (CH3)2CO, at 298 K, 933 J of heat is required. What is the enthalpy of vaporization of acetone in kJ/mol?
Solution:
1 kJ 1000 J = 1mol (CH 3 ) 2 CO 1.75 g (CH 3 ) 2 CO x 58.08 g (CH 3 ) 2 CO 933 J x

H vapor

= 31.0 kJ/ mol (CH3)2CO

Condensation:

Condensation is the passage of molecules from the gaseous state to the liquid state. In turn, the conversion of a gas or vapor to a liquid is called condensation, that is the reverse of vaporization.
H condensatioon = H liquid H vapor = H vap

Condensation is an exothermic process. H condensatioon is always negative.

Vapor pressure:

The pressure exerted by a vapor in dynamic equilibrium with its liquid is called vapor pressure.

Liquid with high vapor pressures are said to be volatile, and those with very low vapor pressures are nonvolatile. The weaker the intermolecular forces, the more volatile the liquid (the higher its vapor pressure). Vapor pressure increases with temperature.
Boiling and the boiling point:

The pressure exerted by escaping molecules equals that exerted by molecules of the atmosphere, and boiling is said to occur.

Normal boiling point:

The pressure at which the vapor pressure of a liquid is equal to standard atmospheric pressure (1 atm = 760 mmHg) is the normal boiling point.

The critical point:

If a liquid in a glass tube is heated, the followings are observed. 1. 2. The density of the liquid decreases; that of the vapor increases; and eventually the two densities become equal. The surface tension of the liquid approaches zero. The meniscus between the liquid and vapor becomes less distinct and eventually disappears.

The critical point refers to the temperature and pressure where a liquid and its vapor become identical. It is the highest temperature point on the vapor-pressure curve. The temperature at the critical point is the critical temperature, Tc and the pressure is the critical pressure, Pc .

The critical point represents the highest temperature at which the liquid can exist. A gas can be liquefied only at temperatures below its critical temperature,Tc. If room temperature is below Tc, this liquefaction can be accomplished just by applying sufficient pressure. If room temperature is above Tc , added pressure and lowering of temperature to a value below Tc are required.
Example: 6.2

As a result of a chemical reaction, 0.132 g H2O is produced and maintained at a temperature of 50.0C in a closed flask of 525 ml volume. Will the water be present as vapor only or as liquid and vapor in equilibrium?
Solution:

First, calculate the pressure that would exist if the water were present as vapor only.

P=

nRT V
1 1 18.02gH 2 Ox0.08206Latm mol K x 323.2K 0.525L 760 mmHg 1 atm = 281mmHg 1mol H 2 O

0.132g H 2 Ox P= P = 0.370atm x

The calculated pressure (281 mmHg) exceeds the vapor pressure (92.5 mmHg), some of the vapor must condense to liquid. The water is present as liquid and vapor in equilibrium at 92.5 mmHg.

Clausis-Clapeyron equation:
7.0 6.5 6.0

aniline
C6H7N

diethyl ether C4H10O

lnP

5.5 5.0 4.5 4.0

Water
H2 O

benzene
C 6H 6

2.0

2.2

2.4

2.6

2.8 3.0 1/T x 103

3.2

3.4

3.6

3.8

Figure 6.2 Vapor pressure data plotted as in lnP vs. 1/T.

1. A particular common form of a vapor-pressure equation is that shown below, which express the relationship of a straight line plotted for the liquids.
1 ln P = A + B T

(6.1)

2. To use equation (6.1), we need to have values for the two constants, A and B. A is related to the enthalpy of vaporization of the liquid: A = H vap /R and it is customary to eliminate B by rewriting (6.1) in a form called ClausiusClapeyron equation.
ln P2 H vap 1 1 = P1 R T1 T2

3. For benzene at 60C, the vapor pressure is 400 mmHg; ln P = ln 400 = 5.99. T = 60 + 273 = 333 K; 1/T = 1/333 = 3.00 x 10-3 ; 1/T x 103 = 3.00. The point corresponding to (3.00, 5.99) is marked by the arrow ( ).
Example: 6.3

Calculate the vapor of water at 35.0C with the following data. T2 = 40.0C, P2 = 55.3 mmHg, H vap = 44.0 kJ/mol.
Solution: Let P1 be the unknown vapor pressure at 35.0C,

T1 = 308.2 K. Substitute the given values into the equation,

55.3 mmHg 44.0 x 10 3 J mol 1 1 1 1 ln = K P1 8.3145 J mol 1 K 1 308.2 313.2

= 5.29 x 103 (0.003245 - 0.003193)

= 0.28 Next, determine that e0.28 = 1.32. Thus,

55.3 mmHg = 1.32 P1

P1 = 55.3 mmHg/1.32 = 41.9 mmHg

6.2 Intermolecular forces and some properties of solids

Melting point and heat of fusion

As a crystalline solid is heated, its atoms, or molecules vibrate more vigorously. Eventually a temperature is reached at which these vibrations disrupt the ordered crystalline structure; atoms, ions, or molecules can slip past one another; the solid loses its definite shape and is converted to a liquid. This process is called melting or fusion.
Melting is the transition of a solid to a liquid and occurs at the melting point. The temperature at which the process of melting occurs is the melting point. The reverse process of melting point, the conversation of a liquid to a solid, is called freezing point.

The melting point of a solid and the freezing point of its liquid are identical. At this temperature solid and liquid coexist in equilibrium.
Sublimation

Like liquids, solids can also give off vapors, although because of the stronger intermolecular forces present, solids are generally not as volatile as liquids at a given temperature.
The direct passage of molecules from the solid to the vapor state is called sublimation. The reverse process of sublimation, the passage of molecules from the vapor to the solid state, is called deposition.

When sublimation and deposition occur at equal rate, a dynamic equilibrium exists between a solid and its vapor. The vapor exert a characteristic pressure called the sublimation pressure.
The enthalpy of sublimation is the quantity of heat needed to convert a solid to vapor.

H2O(s) H2O(l) H2O(s)

H2O(l) H2O(g) H2O(g)

H fus = 6.01 kJ/mol

H vap= 44.92 kJ/mol

H sub = 55.93 kJ/mol

H sub = H vap + H fus

6.3 The van der Waals forces

van der Waals forces is a term used to describe, collectively, intermolecular forces of the London type and interactions between permanent dipoles.

These forces are the ones account for in the vander Waals equation for nonideal gases. The van der Waals equation is an equation of state for nonideal gases. It includes correction terms to account for intermolecular forces of attraction and for the volume occupied by the gas molecules themselves.
Instantaeous and induced dipoles

An instantaneous dipole is an atom or molecule with a separation of charge produced by a momentary displacement of electrons from their normal distribution. An induced dipole is an atom or molecule in which a separation of charge is produced by a neighboring dipole.
Dispersion (London) forces are intermolecular forces associated with instantaneous and induced dipoles.
+ + +

(a)

(b)

(c)

Figure 6.3 Instantaneous and induced dipoles.

Normal condition: A nonpolar molecule has a symmetrical charge distribution. Instantaneous condition: A displacement of the electronic charge produces an instantaneous dipole with a charge separation represented as [ ], [ ].
+

Induced dipole: The instantaneous dipole on the left induces a charge separation in the molecule on the right. The result is a dipoledipole attraction.

Mollecular shapes and Polarizability Polarizability describes the ease with which the electron cloud in an atom or molecule can be distorted in an electric field, that is, the ease with which a dipole can be induced.

The relations of the polarizability to the molecular mass and molecular shapes are addressed by the followings.
Polarizability: (i) no. of e-- mol. mass

(ii) molecular shape Polarizability increases with increased number of electrons, and the number of electrons increases with increased molecular mass. In large molecules some electrons, being farther from atomic nuclei, are less firmly. These electrons are more easily displaced and the polarizability of the molecule increases. Because dispersion forces become stronger as polarizability increases, melting point and boiling point of covalent substances generally increase with increasing molecular mass. (2) The strength of dispersion forces also depends on molecular shape. For instant, the elongated pentane molecule is more easily polarized than the compact neopentane molecule. Intermolecular forces are stronger in pentane than in neopentane. Thus boiling point of Pentane is higher than that of neopentane.
H H H H C H H C H H C C H H C H H H H C H H C H H H C H C H H C H H

(a) Neopentane Bpt = 9.5C

(b) Pentane Bpt = 36.1C

Dipole-dipole attraction

In a polar substance, molecules try to line up with the positive end of one dipole directed toward the negative ends of neighboring dipoles. This additional ordering of molecules can cause a substance to persist as a solid or liquid at temperature higher than otherwise expected. Consider N2, O2, and NO. There are no electronegativity differences in N2 and O2 and both substances are nonpolar. In NO, on the other hand, there is an electronegativity difference and the molecule has a slight dipole moment. Hence, NO has the highest boiling point of the three as shown below. N2 = 0 (nonpolar) Mol.mass 28 u Bpt 77.34 K NO =0.153 D (polar) mol.mass 30 u Bpt 121.39 K O2 =0 (nonpolar) mol.mass 32 u Bpt 90.19 K

Summery of van der Waals forces

When assessing the important of van der Waals forces, consider the following. 1.
Dispersion (London) forces involve displacement of all the electrons in molecules. The strengths of these forces increase with increased molecular mass and also depend on molecular shapes. Dispersion forces exist between all molecules. 2. Forces associated with permanent dipoles involve displacement of electron pairs in bonds rather than in molecules as a whole. They are found only in substances with resultant dipole moments. Their existence adds to the effect of dispersion forces also present.

3. When comparing substances of roughly comparable molecular masses, dipole moment can produce significant differences in such properties as melting point, boiling point, and enthalpy of vaporization. 4. When comparing substances of widely different molecular masses, dispersion forces are usually more significant than dipole forces.

It may be described how these statements relate to the data including a rough breakdown of van der Waals forces into dispersion forces and those due to dipoles for the selected substance: F2, HCl, HBr, HI as follows. (i) HCl and F2 have comparable molecular mases, but because HCl is polar it has significant larger H vap and a higher boiling point than does F2. (ii) Within the series HCl, HBr, and HI, molecular mass increases sharply, and H vap and boiling points increase in the order: HCl < HBr < HI.
Hence, H vap and boiling points of the all substances are in increasing order of F2, HCl, HBr, HI.
Example: 6.4

Which would you expect to have the higher boiling, the hydrocarbon fuel butane, C4H10, or the organic solvent acetone (CH3)2CO?
Solution:

They have the same molecular mass (58u). So we base our prediction on some other factors: 1. 2. The electronegativity difference between C and H is so small that H/C is generally nonpolar. The acetone molecule has strong C to- O bond moment . Acetone has a resultant dipole moment and is a polar molecule.
Thus, the polar substance acetone has the higher boiling point.
Practice example:

Arrange the following substances in the order in which you would expect their boiling points to increase: CCl4, Cl2, ClNO, N2.

6.4 Hydrogen bonding A hydrogen bond is formed when an H atom bonded to one highly electronegative atomF, O, or Nis simultaneously attracted to a small highly electronegative atom of a neighboring molecule. Hydrogen bonds are rather strong intermolecular forces, with energies of the order of 15 to 40 kJ/mol. In hydrogen bond formation, the highly electronegative atom to which an H atom is covalently bonded pulls an electron pair away from the H nucleus, a proton. This leaves the proton unshielded, and it is attracted to a lone pair of electrons on a highly electronegative H atom of a neighboring molecule. Hydrogen O O H bonding atom can occur only with H atoms because H all other atoms have inner-shell electrons to shield H H O H H their nuclei. Thus, hydrogen bonding is unique O to certain hydrogen-containing compounds. H Ordinary water is certainly the most common O H H substance in which hydrogen bonding occurs. Figure mentioned above shows how one water molecule is held to four neighbors in a tetrahedral arrangement by hydrogen bonds. In ice, hydrogen bonds hold the water molecules in a rigid but rather open structure. As ice melts, only a fraction of the hydrogen bonds are broken. One indication of this is the relatively low heat of fusion of ice (6.01 kJ/mol). It is much less than we would expect if all the hydrogen bonds were to break during melting. At the melting point, water molecules are packed more tightly in liquid water than in ice. This is why the liquid is more less than ice. When liquid water is heated above the melting point, hydrogen bonds continue to break. The molecules become even more closely packed, and the density of the liquid water increases. Liquid water attains its maximum density at 3.98 C. Above this temperature the water behaves in a normal fashion: its density decreases with temperature.

This behavior explains why a freshwater lake freezes from the top down. When the water temperature falls below 4C, the more dense water sinks to the bottom of the lake and the colder surface water freezes. The ice at the top of the lake then tends to insulate the water below the ice from further heat loss.
6.5 Chemical Bonds As Intermolecular Forces

Network Covalent Solids

Covalent bonds extend throughout a crystalline solid. In these cases the entire crystal is held together by strong forces. The best examples are described as follows.
Diamond:

Each atom is bonded to four others. The type of hybridization scheme that corresponds to four bonds directed from a central atom to the corners of a tetrahedron is sp3. When viewed from a particular direction, a nonplanar hexagonal arrangement of carbon atoms is also seen [shown in Figure 6.4 (a)]. Both diamond and silicon carbide (silicon atoms are substituted for onehalf the carbon atoms) are nonconductors of electricity and do not melt until very high temperatures are reached. SiC sublimes at 2700C, and diamond melts above 3500C.
Figure 6.4 The diamond

structure.

(a) A potion of Lewis (b) Crystal structure. atom is bonded to tetrahedral fashion. the entire crystal called a unit cell.
(a)

structure. Each carbon four others in a The segment of shown here is

(b)

Graphite:

In graphite the bonding involves the orbital set sp2+p. The three sp2orbitals are directed in a plane at angles of 120. The p orbital is perpendicular to the plane, directed above and below it. These orbitals are the same ones used for carbon atoms in benzene, C6H6.

This type of bonding produces the crystal structure shown in Figure 6.5. Each carbon atom forms strong covalent bonds 142 pm with three neighboring carbon atoms in the same plane, which gives rise to layers of carbon atoms in a hexagonal arrangement. The p electrons of the carbon atoms are delocalized. Bonding within layers is strong, but between layers it 335 pm is much weaker. The CC bond distance within a layer is 142 pm (compared to 139 pm in benzene); between layer it is 335 pm.
Figure 6.5 The graphite structure.

Because of weak bonding between layers, the layers can glide over one another rather easily. As a result graphite is a good lubricant, either in dry form or suspended in oil. Because of the delocalized p electrons, they migrate through the planes of carbon atoms when an electric field is applied; graphite conducts electricity. Diamond is not an electrical conductor because all of its valence electrons are localized or permanently fixed into single covalent bonds.
Interionic Forces

To predict properties of an ionic solid we face the lattice energy of the crystal, depending to some extent on the type of crystal structure, the following generalization works well.
Lattice energy is the quantity of energy released in the formation of one mole of a crystalline ionic solid from its separated gaseous ions.

The attractive force between a pair of oppositely charged ions increases with increased charged on the ions and with decreased ionic sizes.

Ionic solid do not melt at ordinary temperature. We can melt ionic solid by supplying enough thermal energy to disrupt the crystalline lattice.
The higher the lattice energy is, the higher is the melting point.

To dissolve an ionic compound, the energy required to break up an ionic crystal results from the interaction of ions in the crystal with molecules of the solvent (e.g., water molecules).
In general, the lower the lattice energy is, the greater is the quantity of an ionic solid that can be dissolved in a given quantity of solvent.

This idea is illustrated through Figure 6.6.

Relative attractive force:
Na+

Mg2+ ClO2-

Radius:

Na+ = 95 pm Cl- = 181 pm

Mg2+ = 65 pm O2- = 140 pm

Radius sum = distance between center of ions:

276 pm

205 pm

Figure 6.6 Interionic forces of attraction.

Because of the higher charges on the ions and the closer proximity of their centers, the interionic attractive force between Mg2+ and O2- is about seven times as great as below Na+ and Cl-.
Example: 6.5

Predicting Physical Properties of Ionic Compounds. Which has the higher melting point, KI or CaO?
Solution:

Ca2+ and O2- are more highly charged than K+ and I-. Also Ca2+ is smaller than K+ and O2- is smaller than I- The lattice point of CaO is much larger than KI, thus CaO should have the higher melting point.

6.5 Crystal structures

Crystal Lattice

To describe the structures of crystal, we have to work with threedimensional patterns, three sets of parallel planes called a lattice.
The planes are equidistant an mutually perpendicular (intersect at 90 angles). This is called the cubic lattice.
Unit cell is a small collection of atoms, ions, molecules from which an entire crystal structure can be inferred. A body- centered cubic (bcc) crystal structure is one in which the unit cell has structure units at each corner and one in the center of the cube.

A face-centered cubic (fcc) crystal structure is one in which the unit cell has structural units at the eight corners and in the center of each face of the unit cell. It is derived from the cubic closest packed arrangement of spheres.

(a) Simple cubic

(b)

(c)

Body-centered cubic. Face-centered cubid.

Figure 6.6 Unit cells in the cubic crystal system.

In the top row only the centers of spheres (atoms) are shown at their respective positions in the unit cells. The space--filling models in the bottom row show contacts between spheres (atoms). In the simple cubic cell,

spheres come into contact along each edge. In the bodycentered cubic (bcc) cell, contact of the sphere is along the cube diagonal. In the faced-centered cubic (fcc) cell, contact is along the diagonal of a face.

Closest packed structures

A octahedral hole
ral B hed B tra er e A er t lay cov les in ho hexagonal closest packed cov er hole octahe A dr s in laye al C rB B A

tetrahedral hole

cubic closest packed

Figure 6.7 Closest packed structures.

Hexagonal closest packed ways in which spheres can be minimize the amount of free among them. The crystal on this type of packing is hcp.

is one of the two packed to space or voids structure based referred to as

In the Figure a unit cell is

highlighted

in

heavy black. The atoms that are part of the cell are in solid color. The unit cell is not a tube. Three adjoining unit cells are also shown. The united cell and broken-line regions together show the layering (ABC).
Cubic closest packed is one of the two ways in which spheres can be packed to minimize the amount of free space. Table 6.1 Some features of close-packed structures in metals.

Crystal structure
hcp fcc bcc

Crystal coordination number 12 12 8

No.atoms per unit cell 2 4 2

Examples

Cd, Mg, Ti, Zn Al, Cu, Pb, Ag Fe, K, Na, W

Crystal coordination number (CCN) and number of atoms per unit cell

The crystal coordination number signifies the number of nearest neighboring atoms (or ions of opposite charge) to any given atom (or ion) in a crystal.

For the bcc structure: this is 8. Only the center atom belongs entirely to the bcc unit cell. The corner atoms are shared among 8 adjoining unit cells. Only one eighth of each corner atom should be thought of as belonging to a given unit cell. Thus , the eight corner atoms collectively contribute the equivalent of one to the unit cell. The total number of atoms in a bcc unit cell is two [1 + (8 x 1 )]. 8

For the hcp unit cell: CCN is 12. We also get 2 atoms per unit cell. The corner atoms account for ( 1 x 8) = 1 atom and the central atom 8 belongs entirely to the unit cell. In the fcc unit cell: CNN is 12. The corner atoms account for ( 1 x 8) = 8 1 1 atom and those in the center of the faces for ( 2 x 6) = 3 atoms. The fcc unit cell contains four atoms.

X-rays diffraction

Cry
Lead shield X-ray tube Photographic film

Figure 6.8 Diffraction of X-rays by a crystal.

When a beam of X-rays encounters atoms, X-rays interact with electrons in the atoms and the original beam is reradiated, diffracted (scattered) in all directions. The scattered X-rays produce a visible pattern on a film.

detector

d sin

planes of atoms or ions

Figure 6.9 Determination of crystal structure by X-ray diffraction.

Two rays in the monochromatic X-ray beam, labeled (a) and(b), diffracted to the parallel planes of atoms in a crystal.
o o o

Wave (a) is reflected by one plane of atoms or ions in a crystal and wave (b) from the next plane below. Wave (b) travels a greater distance than wave (a). The additional distance is 2d sin . that additional distance travel by wave (b) equal an integral (n) multiple of the wavelength of the X-rays ().
n = 2d sin .

(d = spacing between atomic planes).

Example: 6.6 Using X-ray data to determine an atomic radius.

At room temperature ion crystallizes in a bcc structure. to Figure 6.9 is found to be 287 pm. What is the the radius of an iron atom?

l = 287 pm

Figure 6.9 Determination of the atomic radius of iron. The right triangle must conform to the formula: a2 + b2 = c2. That is (l)2 + (l 2 )2 = ( )2,or l2 + 2 (l)2 = 3 (l)2. l 3 Solution:

4r

Pythagorean

Nine atoms are associated with a bcc unit cell, one of eight is located at each of the eight corners of the cube and one at the center. The 3 atoms along a cube diagonal are in contact.

The diagonal of a cube =l 3 The length of an edge, l = 287 pm

4r = l 3
r= 3 x 287pm = 124 pm 4

Example: 6.7

Al crystallizes in a fcc structure. Given that the atomic radius of Al is 143.1 pm. What is The volume of a unit cell?
Solution:

For the fee structure, 4r = l 2 r= 2 /4 x 143.1 pm

V = r3 = 6.628 x 107 (pm)3

Example: 6.8

Use data from Example 6.6, calculate the densitv of iron.

Solution:

1 = 287 pm = 287 x 10-10 cm. V = I3 = (2.8 x 10-10)3 cm3 = 2.3639 x 10-23 cm3/ unit cell d= 55.85g 1 mol 2 atom 1 unit cell = x x 23 1mol 6.02 x 10 atms 1 unit cell 2.3639 x 10-23 cm3

= 7.86 g/cm3 Ionic crystal structure

The relative size of cations and anions are important in establishing a particular packing arrangement. .In defining a unit cell of an ionic crystal we must choose a unit cell that
1. by Translation in three dimensions generates the entire crystal; 2. indicate the crystal coordination numbers of the ions; 3. is consistent with the formula of the compound.

To establish the crystal coordination number in an ionic crystal count the number of nearest neighbor ions of opposite charge to any given ion in the crystal.
Note:

The Na ion in the center of 'unit cell is surrounded by six Cl- ions. the crystal coordination number of both ions are six. (By contrast, for Cs' and Ct are eight). We must apportion the 27 ions in each unit cell. Each Cr ion in a corner position is shared by eight unit cells, and each Cl- jn the center of a face is shared by two unit cells. Total number of Cl- ion in a unit cell is (8 x 1/2) + (6 x 1/2) = 1 + 3 = 4. There are 12 Na+ ions along the edges of the unit cell, and each edge is shared by tour unit cells. The Na+ ion in the very center of the unit cell belongs entirely to that cell, the total number of Na+ ions in the Unit cell is (12 x 1/4) (1 x 1) = 3 + 1 The unit cell has the equivalent of Na+ and Cl- ions. The ratio of the two is 4:4 = 1:1, corresponding to the formula NaCI.

Figure 6.10. (a)The NaCI unit cell, (b)The CsCI unit cell Example: 6.9

Relating ionic radius and the dimension of a unit cell of an ionic crystal. The ionic radius of Na+ and Cl- in NaCI are 95 and 181 pm respectively. What is the length of the unit cell of Na Cl?
Solution: along each edge of two unit cell [Figure 6.10 (a)] two Cl- ions are in contact with. one Na+. Hence,

The edge length = (rci) + ( rNa+) + ( rNa+) + (rci) = 2 ( rNa+) + 2 (rci) = [(2 x 95) + (2 x 181)] .= 552 pm
6.6 Lquid crystals

Liquid crystal are a form of 'matter with some of the properties of a liquid and some of a crystalline solid.

Liquid crystals have the fluid properties of liquids and the optical properties of solids. Liquid crystals are observed more commonly in organic compounds that have cylindrically shaped (rod-like) molecules with masses of 200 to 500 u and lengths four to eight times their diameters. Liquid crystals occur widely in living matter.

cell membranes and certain tissues have structures that can be described as liquid crystalline. Hardening of the arteries is caused by the deposition of liquid crystalline compounds of cholesterol. Liquid crystalline properties' have also been identified in various synthetic polymers. Three forms of liquid crystals described as follows.

In the nematic (meaning threadlike) form of the liquid crystalline state, the rodlike molecules 'are arranged in a parallel fashion. They are free to move in all directions but they can rotate only on their long axes. In the smectic (meaning greaselike) form, rodlike molecules are arranged in layers, with the long axes of the molecules perpendicular to the plane of the layers. The molecular motions possible here are translation within but not between layers and rotation about the long axis.
The cholesteric form is related to the nematic form, but molecules are stratified into: layers. The molecular orientation in each layer is different from that in the layer immediately above and below it.

CHAPTER 7 7. Basic concepts of Chemical Bonding

7.1 Ionic bond

Electrons are transferred from one atom to another to form positive and negative ions, which attract each other through electrostatic forces called ionic bonds.
Na + Cl Na + Cl

Example: 7.1

Write Lewis structures for the following compounds. a. BaO b. MgCl2

Solution: a.
Ba + O Na + O

b.

7.2 Covalent bond

Two or more pairs of electrons are shared between atoms; this sharing of electrons is called a covalent bonds.
H

Cl

Cl

Electrons are transferred or shared in a way that each atom acquires an especially stable electron configuration. Usually this is a noble-gas configuration, one with eight outer-shell electrons or an octet.

Multiple covalent bonds

O O

Bond order

The term bond order describes whether a covalent is single (B.O=1), double (B.O=2), triple (B.O=3). The higher the bond order, that is, the more electrons present, the more tightly the atoms are held together.

Bond length

sBond length is the distance between the centers of two atoms joined by a covalent bond. Double bond between atoms is shorter than a single bond and a triple bond is the shortest.
Hydrazine Dinitrogen difluoride Nitrogen
H2N NH2
FN NF
N N

145 pm 123 pm 109.8 pm

Covalent radius

The single bond radius is one-half the distance between the centers of identical atoms joined by a single bond.

Polar covalent bond

A covalent bond in which electrons are not shared equally between two atoms is called polar covalent bond.
H H H polar Cl

Nonpolar

Electronegativity: EN

The more metallic element has lower its EN. The more nonmetallic element has higher its EN.
Example: 7.2

Assessing electronegativity differences and polarity of bonds. a. Which bond is more polar, H Cl or H O? b. Which bond has the greater ionic character?
Solution:

a.

ENH = 2.2; ENCl = 3.2; ENO = 3.4; For the H Cl bond, EN = 3.2 - 2.2 = 1.0 For the HO bond, EN = 3.4 - 2.2 = 1.2. Because its EN is somewhat greater, we expect the HO bond to be the more polar bond.

b.

H O Bond has the greater ionic character than HCl

bond

due to its greater EN value. 7.3 Writing Lewis structures

i. ii.

The strategy for writing a variety of Lewis structures may be described as follows. Determine the total umber of valence electrons in the structure. Write the skeleton structure, and join the atoms in this structure by single covalent bonds.

iii. For each single bond thus formed, subtract two from the total number of valence electrons. iv. With the valence electrons remaining, first complete the octet of the terminal atoms. Then, to the extent possible, complete the octets of the central atom (s). v. At this point, if the central atom (s) lack an octet, from multiple covalent bonds by converting lone-pair electrons from terminal atoms into bonding pairs. Example: 7.3:

Write the Lewis structure of HCN.

Solution:

o o o

Total no. of v.e-s = H (1) + C (4) + N (5) = 10 e-s.

H C N

4 v.e-s used for 2 single bonds, so 6 v.e-s remaining for the octet of N atom, H C N (Incorrect)
H C N H C N

Formal charge: FC

Formal charges are apparent charges associated with some atoms in a Lewis structure. FC = no. Valence electrons 1 (no. Bonding electrons) 2

No. Lone pair electrons In writing Lewis structure, we strive for a structure with no formal charges, but failing this, we seek to keep formal charges to a minimum, generally achieving this object by noting that
a. Where formal charges are required, these should be as small as possible. b. Negative formal charges usually appear on the most electronegative atoms and positive formal charges on the least electronegative atoms.

c. The sum of the formal charges of the atoms in a Lewis structure must equal zero for a neutral molecule and must equal the ionic charge for a polyatomic ion.

These rules on formal charges also lead to the result that the central atom in a structure is generally the atom with the lowest electronegativity.
Example: 7.4

Assign formal charges to the atoms in the following species and then select the more likely skeleton structure.
A. H2NOH or H2ONH Solution: B. SCS or CSS C. NClO or ONCl

A.

H H N O H (i) no formal charge

+1 -1

H N O H (ii)

The more likely skeleton structure is (I). B.

C S (i) no formal charge S
-2 +2

S S (ii)

The more likely skeleton structure is (I). C.

-2 +2

Cl O (i)

O N Cl (ii) no formal charge

The more likely skeleton structure is (I).

7.4 Resonance The situation in which two or more plausible Lewis structure can be written but the correct can not be written at all is called resonance.

The true structure is a resonance hybrid of plausible contributing structures.

O S S O O O Resonance structure S O O Hybrid structure or true structure

7.5 Exceptions to the octet rule Odd electron species

If the number of valence electrons in Lewis structure is odd there must be an unpaired electron somewhere in the structure. For NO molecule, this electron is put on the N atom to obtain a structure free of formal charges.
N O

The present of unpaired electrons causes odd-electron species to be paramagnetic. Molecule with an even number of electrons are expected to have all electrons paired and to be diamagnetic. Highly reactive molecular fragments with one or more unpaired electrons are called free radicals, for instance, the Lewis structure of the two free radicals are
H H C H O H

Incomplete octet

The representation of BF3 is a resonance hybrid based on four contributing structures, including one with an incomplete octet.
(-1) (+1) (+1) (-1) (-1)

F B F F

F B F F

F B F F

F B F F
(+1)

The contributing structures with B to F double bonds have formal charges of 1 on B and +1 on F, contrary to the rules The Lewis structure with the incomplete octet has no formal charges. Characteristic of BF3 . structure is its strong tendency to form a

coordinate covalent bond with a species capable of donating an electron pair to the B atom. This can be seen in the formation of the BF 4 - ion.

F F

F F F B F F

B F

Expanded octets

Nonmetal of the second period have only s and p subshell. The energy different between 2 p and 3 s is too great. The central has only eight electrons an octet. Nonmetal in the third period and beyond contain a d subshell. The energy different between the np and nd is not that great and this open up the possibility of Lewis structures with more than eight electrons around the central atom.

F Cl P Cl
octet

F S

F O F

O S O
expanded octet

Cl F

expanded octet

7.6 The shape of molecules Valence-shell electron-pair repulsion (VSEPR) theory

Electron pairs repel one another, whether they are in chemical bonds (bonding pair) or unshared (lone pairs). Electron pairs assume orientations about an atom to minimize repulsions.

The valence-shell electron-pair repulsion theory focuses on pairs of electrons in the valence electronic shell. This, in turn, results in particular geometrical shapes for molecules.

Applying VSEPR theory

Let us use this four step procedure for predicting the shapes of molecules.

1. Draw a plausible Lewis structure of the species (molecule or polyatomic ion). 2. Determine the number of electron-pair around the central atom and identify them as being either bonding pairs or lone pairs. 3. Establish the electron-pair geometry around the central atom: linear, trigonal planar, tetrahedral, trigonal, bipyramidal, or octahedral. 4. Determine the molecular geometry from the positions around the central atom occupied by the other atomic nuclei, that is, from data in table 4.1.

Table 7.1 Molecular geometry as a function of e--pair geometry Table 7.1 (Continued)

Example: 7.5

Using VSEPR theory to predict a geometrical shape. Predict the molecular geometry of the polyatomic anionICl4-.
Solution:

Apply the four steps outlined above. 1. Write the Lewis structure. The number of valence e-s is
From I. From Cl. To establish ionic charge of (1) (1 x 7) + (4 x 7) + 1 = 36

To join 4Cl atoms to the central I atom and to provide octet for all the atoms we need 32 e-s. We must place the four additional eatom, which has an expended octet. two lone pairs, it does not matter show them around the I atom in the

Cl I Cl

Cl Cl

- s around the I
Because these are exactly how we Lewis structure.

2. There are six electron pair around the I atom, 4 bonding and 2 lone pairs. 3. The electron pair geometry, orientation of 6 electronoctahedral. anion is of the Cl 4. The which according to Table molecular geometry that is
Dipole moment :

that is, pairs,

the is

Cl

ICl4-

Cl Cl
type AX4E2, 4.1 leads to a square planar.

Dipole ment, , is the product of a charge () and distance (d): bond length. = .d Unit: D (Debye) -30 1 D = 3.34 x 10 Coloumb-meter (C.m)

Example:7.7

Determine the relationship between geometrical shapes and the resultant dipole moments of molecules. Which of these molecules would you expect to be polar? Cl2, ICl, BF3, NO, SO2, XeF4.

Solution: Polar: ICl, NO, SO2. ICl and NO are diatomic molecules with an electronegativity difference between the bonded atoms. SO2 is the bent molecule with an electronegativity difference between the S and O atoms. Nonpolar: Cl2, BF3, XeF4.. Cl2 is a diatomic molecule of identical atoms; hence no electronegativity difference. For BF3 and XeF4 refer to Table 4.1. BF3 is a symmetrical planar molecule (120 bond angles). The BF bond moments cancel each other. XeF4 is a square planar molecule with the F atoms arranged symmetrically around the Xe atom. Practice example:

Only one of the following molecule is polar. Which is it, and why? SF6, H2O2,C2H2.
Bond energy

Energy is released when isolated atoms join to form a covalent bond. Exothermic (-). Energy is absorbed to break apart covalently bonded atoms. Endothermic (+)
Bond dissociation energy

Bond dissociation energy, D, is the quantity of energy required to break one of covalent bonds in a gaseous species. Unit: kJ mol- (SI)

2H (g) H2 (g)

H2 (g) 2(H) (g)

H = - 435.93 kJ H = + 435.93 kJ

Double bonds have higher bond energies than single bonds between the same atoms, but they are not twice as large. Triple bonds are strong still but they are not three times as larg.

Enthalpy of reaction: H
Hrxm = H (bond breakage) + H (bond formation)

BE

( reac tan ts )

BE ( products)

Example: 7.8

Calculating an enthalpy of reaction from bond energies. The reaction of methane (CH4) and chlorine produces a mixture of products called chloromethanes. One of these monochloromethane, CH3Cl, used un the preparation of silicones. Calculate H for the reaction. CH4 (g) + Cl2 (g)
Solution:

CH3Cl (g) + HCl (g)

We would break four CH bonds and one ClCl bond and form three CH bonds, one CCl bond, and one HCl bond. The net change is the breaking of one CH bond and one ClCl bond, followed by the formation of one CCl bond and one HCl bond. H for net bond breakage: 1 mol C-H bonds = + 414 kJ 1 mol Cl-Cl bonds = + 243 kJ sum: = + 657 kJ H for net bond formation: 1 mol Cl-Cl bonds = - 339 kJ 1 mol H-Cl bonds = - 431 kJ sum: = - 770 kJ Enthalpy of reaction:
Lattice energy
Hrxm = 657 770 = - 113 kJ

7.7 Energy chages in the formation of ionic crystals

It is the energy given off when separated gaseous ion (positive and negative), come together to form 1 mol of a solid ionic compound.

________________________________ Na+(g) + Cl (g) ________________________

H2 Na
+ (g)

H3

H4

__________________ Na+(g) + Cl-(g)

1 Cl2 (g) 2 1 Cl2 (g) 2 1 Cl 2 (g) 2 H6

________________________
H1 Na (g) +

H5

________________________ Na (s) +

__________________ NaCl (s)

Figure 7.1 Enthaipy diagrtam for the formation of an ionic crystal. A six step cycle for NaCl is illustrated here that begins with Na (s) and Cl 2 (g) and return to the starting point. For the overall cycle ,
H1 +

H2 + H3 + H4 + H5 + H6 = 0

Formation of an ionic crystal is represented through the first five steps. The six steps and their enthalpy changes for NaCl are written below, and the enthalpy changes are identified in terms of the property they represent.
1. Na (s) 2. Na (g) 3.
1 Cl2 (g) 2

Na (g)

H1 = Hsublimation = +108 kJ

Na+(g)+e- H2 = 1.st ion.energy= +496 kJ Cl(g)

H3=
1 2

Cl-Cl bond energy

= +122 kJ
4. Cl(g)+ e5. Na+(g)+ Cl-(g) 6. NaCl(s)

Cl- (g)

H4 = EA of Cl = -349 kJ

NaCl(s) H5= lattice energy of NaCl=? Na(s)+ Cl2(g)

1 2
H6 = Hf [NaCl(s)]

= +411 kJ
H1 + H2 + H3 + H4 + H5 + H6 = 0

(108 + 496 + 122 349 + H5 + 411) kJ = 0

H5 = lattice energy = (-108 -496 -122 +349 -411) kJ

= -788 kJ

8.2 Metallic bond

The challenge to a bonding theory for metals is to explain how so much bonding can occur with so few electrons. Also, the theory should account for certain properties that metals display to a far greater extent than nonmetals, such as a lustrous appearance, an ability to conduct electricity, and an ease of deformation (metals are easily flattened into sheets and drawn into wires).
The electron sea model

An oversimplified theory that can explain some of the properties of metals just cited pictures a solid metal as a network of positive ions immersed in a sea of electrons. In Li, for instance, the ions are Li+ and one electron per atom is contributed to the sea of electrons. Electrons in the sea are free (not attached to any particular ion) and they are mobile.
Explanation of the metallic properties by electron sea model

Thus, if electrons from an external source enter a metal wire at one end, free electrons pass through the wire and leave the other end at the same rate. In this way, electrical conductivity is explained. Free electrons (those in the electron sea) are not limited in their ability to absorb photons of visible light as are electrons bound to an atom. Thus metals absorb visible light; they are opaque. Electrons at the surface of a metal are able to reradiate, at the same frequency, light that strike the surface, and this explains the lustrous appearance of metals.

The ease of deformation of metals can be explained in this way; If one layer of metal ions is forced across another, perhaps by hammering, no bonds are broken, the internal structure of the metal remains essentially unchanged, and the sea of electrons rapidly adjusts to the new situation . Band theory
1.
Energy band: A set of molecular orbitals with extremely small energy between each pair of successive levels. This of very closely spaced orbital energy levels is

N an separation collection molecular called an

energy band.
2. 3.
Valence band: The highest energy band of molecular orbitals in a metal that is filled with valence electrons is called the valence band. Conduction band: The band of orbitals through which electrons can move is known as a conduction band.
3Li:

1s2, 2s1 2p0

Valence band Conduction band

In a semiconductor, the valence band and conduction band are separated only by a small energy gap; Electrons in the valence band may acquire enough energy (thermal energy) to jump to a level in the conduction band, for example, Si, Ge.

In consequence, the electrical conductivity of semiconductor increases with temperature.

Semiconductors:

Modern electronic components Light-emitting diodes: LED; Solar cell In some of materials (Cds), the energy gap between the valence band and conduction band is fixed size, called intrinsic semiconductors.
Doping:Carefully adding impurities to the extrinsic semiconductor.

[Ne] 3s23p3: 5 valence electrons 2 2 14Si: [Ne] 3s 3p : 4 valence electrons

15P:

If Si is doped with P, P atom enter the Si crystal structure by using four of their valence electrons to bond to Si atoms. One electron promoted to the conduction band for every P atom. This type is called n-type semiconductor. If Si is doped with B atoms, which have only three valence electrons, there is a deficiency of one electron for every B atom. Electrons from the valence band in the crystal move to form four bonds. This creates positive holes in the crystal. Electrons in the crystal can move to filled positively charged holes and semiconductor is called a p-type semiconductor.
sunlight p-type silicon

A thin layer of a ptype semiconductor is in contact with an n-type n-type semiconductor in a region called the silicon junction. When the p-type semiconductor is struck by a beam of light, electrons in the valence band can absorb energy and promoted to the conduction band, creating holes in the valence band. e flow Conduction electrons can easily cross the junction into the n-type semiconductor. This sets up a flow of electrons, an electric current. Electrons can be carried by wire through an external load and eventually returned to the p-type semiconductor, where they fill positive holes. Further light absorption creates more conduction electrons and positive holes, and the process continues as long as light shines on the solar cell.

CHAPTER 9

9. 9.1

Solutions and Their Physical Properties Definition:

A solution: is a homogeneous mixture of solvent and solute. A solvent: is the component that is present in the greatest quantity in a solution. A solute: is a component that is present in lesser quantity than the solvent in a solution. A concentrated solution: has a relatively large quantity of dissolved solute. A dilute solution has a relatively small quantity of dissolved solute.

Gaseous solution:

Air: (N2 + O2 + several other gases). Natural gas: (CH4 + C2H6+ several other gases).
Liquid solution:

Sea water: (H2O + NaCl + many other) Vinegar: (CH3COOH + H2O).

Solid solution:

Brass. (Cu + Zn) Bronze. (Cu + Sn) Solder. (Pb + Sn) Dental amalgam. (Ag + Sn)
Solid solution with a metal as a solvent is also called alloys.

9.2

Expression of concentration

Mass percent =

mass of solute x 100 % mass of solution volume of solute x 100 % volumeof solution

Volume percent =

Mass/volume percent is used in medicine and pharmacy.

Example: 9.1

What mass percent of a solution containing 8 g of NaOH in 70 g of water?

Solution: Mass present =

8.0 g NaOH x100% 78.0 g water

= 10.26 %

Mole fraction: XA =

nA nA + nB

mole of A Total mole of componentin solution

Mole percent = XA x 100 %

 Molarity: M =

mole of solute volumeof solution

[mol/L]

mole of solute Molality: m = [mol/kg-solvent] mass of solvent in kg

Practice Example:

10 mL of ethanol (d = 0.789 g/ml) is made up to 100 mL ethanol water solution by adding water. The resulting solution density is 0.982 g/mL. What is the concentration of ethanol in this solution expressed as? (a) Vol% (b) mass % (c) mass/vol % (d) Ethanol (e) Mol% (f) molarity (g) molality

Solubilities of gases

Solubilitys of gases decrease with increased temperature and increase as the gas pressure is increased.

Henrys law:
The mass of a gas dissolved in a given mass of liquid is directly proportional to the pressure of the gas above the solution. .

C = K. Pgas (C = concentration) C K= Pgas

C C 1= 2 P P 1 2

Note: Gases that are highly soluble in water (NH3,HCl, SO2) do not obey Henrys law.

Example: 9.1

The solubility of N2(g) at STP is 23.54 mL N2/L. Find required gas pressure to increase the solubility of N2(g) to a value of 100 mL N2/L.
Solution:

K = C/Pgas =

23.54 mL N 2 /L 1.00 atm PN

=
2

100.0 mL N 2 /L PN
2

PN = (100/23.54) x 1.000 atm = 4.25 atm

2

9.3
1.

Colligative properties of solutions

Vapor pressure of solution: The vapor pressure of a solution is always lower than the vapor pressure of the solvent at the same temperature. This is because there are fewer solvent molecules per unit area on the surface of the solution. The escaping tendency of the solvent molecules in a solution decreases as the concentration of the non-volatile solute increase. The greater the concentration of non-volatile solute in the solution, the lower the vapor pressure of the solvent.

2. 3.

Psolvent = Psolvent Psolvent

Psolvent = The lowering of vapor pressure. Posolvent = Vapor pressure of the pure solvent. P solvent = Vapor pressure of solvent in the solution.
Raoults Law (1887) of vapor pressure:

The partial pressure exerted by solvent vapor above an ideal solution (PA) is the product of the mole fraction of solvent in the solution (XA) and the vapor pressure of the pure solvent at the given temperature ( PA0 ) .

PA = XA PA0 The lowering of the vapor pressure in dilute solution of nonelectrolytes at constant temperature is proportional to the quantity of substance dissolved in a given weight of solvent.
Example: 9.2

The vapor pressure of pure benzene and toluene at 250C are 95.1 and 28.4 mmHg, respectively. A solution is prepared in which the mole fractions of benzene and toluene are both 0.500. What are the partial pressures of the benzene and toluene above this solution? What is the total pressure?
Solution:

Benzene-toluene solution should be ideal, so we expect Raoults law to both solution components. Pbenz = Xbenz P0benz = 0.500 x 95.1 mmHg = 47.6 mmHg Ptol = Xtol P0tol = 0.500 x 28.4 mmHg = 14.2 mmHg Ptot= Pbenz + Ptol =47.6 mmHg +14.2 mmHg= 61.8 mmHg

Freezing point depression and boiling point elevation of nonelectrolyte solution

Figure 9.1 Vapor pressure lowering by a nonvolatile solute.

Non-volatile solute lowers the vapor pressure of solvent. So a higher temperature is required for the vapor pressure of the solution to become equal to atmospheric pressure. A solution that contains nonvolatile solute always has higher boiling point than pure solvent. Therefore boiling point of the solvent is elevated.

The boiling point raised or the freezing point lowered is proportional to the molar concentration of solute for dilute solutions.
Tb = Kb. m Tf = Kf. m

Tb = Freezing point depression

Tf = Boiling point elevation

Kb and Kf = Proportionality const.

Example: 9.3
Nicotine, extracted from tobacco leaves, is a liquid completely miscible with water at temperatures below 60oC. (a) What is the molality of nicotine in an aqueous solution that started to freeze at 0.450oC? (b) If this solution is obtained by dissolving 1.921 g of nicotine in 48.92 g H2O, what must be molar mass of nicotine? (Kf = 1.86oC m-1)

Solution:

(a) Molality = Tf / Kf.=

0.450C = 0.242 m 1.86C m 1

(b) M = molar mass of nicotine,

Amount of solute in moles = 1.921 g/M Molality = 1.921 g/M = 0.242 mol/kg water
0.04892kg water
M=

1.921 g = 162 g/mol (0.04892 x 0.242) mol Osmosis:

spontaneous solvent semipermeabe of lower into a

Osmosis is the process by which the molecules pass through a membrane from a solution concentration of solute solution of higher concentration of solute.

Osmotic pressure:
A pressure that would have to a solution to stop the passage from the pure solvent through semipermeable membrane into the solution. be applied into of molecules a

n RT = C.RT V

n = The amount of solute in moles V = The volume of solution in liters n/V = C = Molarity of the solution.

Note:

These properties, whose values depend only on the concentration of solute particles in solution and not on what he solute is, are called colligative properties.

Reverse osmosis:
The net flow of water through the membrane will to right. If the pressure greater tan pressure is applied to the flow of water will be formed direction. This is the molecules be formed left osmosis a net reverse condition

right,

known as reverse osmosis.

Solution of electrolyte:
Tb = i x Kb x m

(m = molality of the solute)

Tf = I x Kf x m

= i x C.RT

(i = Vant Hoff factor)

If these equations are used -(i) (ii) for non electrolytes, simply substitute i = 1. For strong electrolytes, predict a value of i is suggested in the following example.

Example:9.3

Predict the freezing point of aqueous 0.00145 m MgCl2.

Solution:

MgCl2(aq)

Mg 2+(aq) + 2Cl-(aq)

Because three moles of ions are obtained per mole of formula units dissolved, we expect the value i = 3.

Tf = i x Kf x m Tf = 3 x 1.86oC m-1 x 0.00145 m

= 0.00810C

CHAPTER 10

Acid Base Theories: 10.1 Arrhenius Theory

An acid is a compound which could produce (H+) in water solution and a base is a compound which could produce (OH-) in water solution .
A neutralization reaction involves the combination of hydrogen ions and hydroxide ions to form water.

HCl

H+ (aq) + Cl- (aq)

2 NaOH Na+ (aq) + OH- (aq)

H+ (aq) + OH- (aq)

an acid a base

H2O
water

10.2

Bronsted and Lowery

An acid is a proton donor and a base is a proton acceptor. HCL + H2O H 3O + + Cl-

HCl is acid, H3O+ is the conjugated acid of H2O. H2O is base, Cl-- is the conjugate base. NH3 + H2O NH4+ + OH-

NH3 is base, NH4+ is the conjugate acid of NH3.

H2O is acid, OH- is the conjugate base. Substances that can act either as an acid or a base, they are said to be amphiprotic.

Example: 10.1

For each of the following identify the acids and bases in both the forward and reverse reactions.
a. b. c. d.

HClO2 + H2O OCl- + H2O NH3 + H2PO4 HCl + H2PO4-

H3O+ + ClO2HOCl + OHNH4+ + HPO4H3PO4 + Cl-

Solution: a. HClO2 loses a proton, H+, to become ClO2-. Therefore, HClO2 is an acid, and ClO2- is its conjugate base. H2O accepts the proton and becomes H3O+. H2O is a base, and H3O+is its conjugate acid.

HClO2 + H2O acid (1) base (2)

H3O+ + ClO2acid (2) base (1)

b. OCl- is a base and gains a proton from water.OH- is the conjugate base of H2O.

OCl- + H2O base (2) acid (1)

c. NH3 + H2PO4-

HOCl + OHacid (2) base (1) NH4+ + HPO4acid (2) base (1)

base (2)

acid (1)

d. HCl + H2PO4-

H3PO4+ Clacid (2) base (1)

acid (1) base (2)

Reactions (a) and (b) show that H2O is amphiprotic Reactions (c) and (d) illustrate the same for H2PO4-.
10.3 Lewis Theory:

A Lewis acid is a species (an atom, ion, or molecules)that is an electron-pair acceptor A Lewis base is a species that is an electron-pair donor.
F F B F + H N H H F F B F H N H H

Lewis acid Lewis base

Salt

10.4

The ionic dissociation of water The self-ionization of water and the pH scale

In the self-ionization of water, for each H2O molecule that acts as an acid, another acts as a base and hydronium in (H3O+) and hydroxide ion (OH-) are formed. This reaction is reversible. H2O + H2O H3O+ + OH-

K=

[H 3O + ][OH + ] [H2O] = const: [H 2O]2

K = [H3O+] [OH-]

The very small electrical conductance of pure water corresponds to the very small [H+] and[OH-]. Both ions have equal concentration, each being 1 x 10-7 mol dm-3. The equilibrium constant for the self-ionization of water is the ion product of water and is symbolized as Kw. At 25oC, Kw = [H3O+] [OH-] = 1 x 10-14. At any other temperature, Kw will have a different values. At 60oC, Kw = 9.6 x 10-14 At 100oC, Kw = 5.5 x 10-13
PH and pOH

PH is the negative of the logarithm of [H+], Restate in terms of [H3O+]. pH = - log [H3O+] pOH = - log [OH-]
Example: 10.2

In a laboratory experiment, student found the pH of (1) a rainwater sample to be 4.35 and (b) a sample of household ammonia to be 11.28. (a) What is [H3O+] in the rainwater ? (b) What is [OH-] in the ammonia ?

Solution: a. By defination, pH = -log [H3O+] or

log [H3O+] = - pH = - 4.35 [H3O+] = 10-4.35 = 4.5 x 10-5 M

b.

First, determine pOH with equation ,

pOH = 14.00 pH = 14.00 11.28 =2.72 pOH = -log [OH-]

log [OH-] = -pOH = - 2.72 [OH-] = 10-2.72 = 1.9 x 10-3 M.

Strong acid and strong base:

(Completely ionized) Strong acids: HCl, HBr, HI, HClO4, HNO3, H2SO4 Srong bases: LiOH, NaOH, KOH, Ca (OH)2, Ba (OH)2,..

Example: 10.3

Calculating ion concentration in an aqueous solution of a strong acid. Calculate [H3O+], [Cl-], an [OH-] in 0.015 M HCl(aq).
Solution:

We can assumed that HCl is completely ionized and is the sole source of H3O+ in solution. Hence, [H3O+] = 0.015 M [Cl-] = [H3O+] = 0.015 M Kw = [H3O+] [OH-] = 1 x 10-14 (0.015) [OH-] = 1 x 10-14

1.0 x 1014 [OH ] = = 0.67 x10-12 = 6.7 x 10-13 M 2 1.5x 10

-

Example: 10.4

Ca (OH)2(s) is soluble in water only to the extent of 0.165 g Ca (OH)2/100.0 ml solution at 20oC ? What is the pH of saturated Ca (OH)2(aq) at 20oC ?

Solution:

0.165g Ca (OH) 2 x
Molarity =

1mol Ca (OH) 2 74.09g Ca (OH) 2 0.100L

= 0.0223 M Ca (OH)2

[OH-]=

0.0223 mol Ca (OH)2 2 mol OH x 1L 1 mol Ca (OH)2

= 0.0446 MOHpOH = -log [OH-] = - log 0.0446 = 1.35 pH = 14.00 pOH = 14.00 1.35 = 12.65

Weak acid and weak base:

pKa = - log Ka (Ka = weak acid ionization const:) pKb = - log Kb (Kb = weak base ionization const:)

Esample:10.5

A 0.250 M aqueous solution of HC4H7O2 is found to have a pH of2.72. determine Ka for butyric acid.
Solution:

At equilibrium, HC4H7O2 + H2O Initial con: Changes: equal conc: (-x M) 0.250 M. (0.250 x) M

H3O+ + C4H7O2--(+x M) + (+x M) xM xM ---

But x is not unknown. It is the [H3O+] in solution, and we can determine this from the pH. Log [H3O+] = - pH = - 2.72 [H3O+] = 10-2.72 = 1.9 x 10-3 = x

Ka =

[H 3O + ][C4 H 7 O 2 ] x.x = [HC4 H 7 O 2 ] 0.1250 x

(1.9x10 3 ) (1.9x10 3 ) = 1.5 x 10 5 = 3 0.250 - (1.9x10 )

Esample:10.6

Show by calculation that the pH of 0.100 M aqueous solution of HC4H7O2 should be about the value shown on the pH meter that is pH 2.8.

Solution:

At equilibrium, HC4H7O2 + H2O Initial con: Changes: equal conc: (-x M) 0.250 M. (0.250 x) M

H3O+ + C4H7O2--(+x M) + (+x M) xM xM ---

[H 3 O + ][C 2 H 3 O 2 ] x.x Ka = = = 1.8 x 10 -5 [HC 2 H 3 O 2 ] 0.100 x

We assumed that (0.100 x) 0.100. x2 = 0.100 x 1.8 x 10-5 = 1.8 x 10-6 x = [H3O+] = 1.8 x 10 -6 = 1.3 x 10-3 M pH = - log [H3O+] = - log (1.3 x 10-3) = -(-2.89) = 2.89

Polyprotic acids:

Acid molecules have more than one hydrogen atom per molecule is known as polyprotic acid. H3PO4 H2PO4HPO42H+ + H2PO4H+ + HPO42H+ + PO43-

10.5

Buffer solution

Buffer solution is a solution whose pH values change only slightly upon the addition of small amounts of either an acid or a base. Common buffer solutions are(i) (ii)

a mixture of a weak acid and its conjugate base or a mixture of a weak base and its conjugate acid.
Acid condition of buffer solution: (pH = 4 to 7)

For example, a mixture of ethanoic acid and sodium ethanoate. CH3COOH(aq) CH3COONa(aq) CH3COO-(aq) CH3COO-(aq)
+ +

H+(aq) Na+(aq)

Alkaline condition of buffer solution: (pH = 7 to 11)

For example, a mixture of ammonium hydroxide and ammonium chloride. NH4OH(aq) NH4Cl(aq) NH4+(aq) + OH-(aq) NH4+(aq) + Cl-(aq)

Now imagine adding a small amount of a strong acid to acidic buffer solution. A reaction occurs in which CH3COO- is converted to its conjugate acid. CH3COO-(aq) + H3O+ CH3COOH(aq)
+

H2O

This prevent a change in pH of the solution. Imagine adding a small amount of a strong base to acidic buffer solution. A reaction occurs in which CH3COOH is converted to its conjugate base CH3COO-. CH3COOH(aq) + OHCH3COO-(aq)
+

H2O

This prevent a change in pH of the solution.

An Equation for Buffer Solution:

(The Henderson-Hasselbalch equation)

Let us consider a mixture of a weak acid (such as CH3COOH) and its salt (CH3COONa), we start with the familiar expression: CH3COOH + H2O H3O+ + CH3COO-

[H 3 O + ][CH 3 COO - ] Ka = [CHCOOH]

[H3O+] = Ka

[CH 3 COOH] [CHCOO - ] [CH 3 COOH] [CHCOO - ]

- log [H3O+] = -log Ka log

[CH 3COO- ] pH = pKa + log [CHCOOH] [conjugate base] [acid] [conjugate acid] [base]

pH = pKa + log

pOH = pKb + log

Example:10.7

Calculate the pH of a buffer solution containing 0.01 mole of ethanoic acid (Ka = 1.8 x 10-5) and 0.1 mole of sodium ethanoate per cm3.
Solution:

For the acid,

CH3COOH [CH 3COO- ] [H + ] Ka = CH3COOH [H+] = 1.8 x 10-5 x

CH3COO- + H+

[CH3COOH] [CH 3COO- ]

[CH3COO-]equil = [CH3COO-]salt+ [CH3COO-]acid sodium ethanoate is completely dissociated and ethanoic acid is negligibly dissociated in the presence of common ion, therefore [CH3COO-]equl = 0.1 [CH3COOH] = 0.01 [H+] = 1.8 x 10-5 x 0.001/0.1 = 5.74

Esample:10.8

What is the pH of a buffer solution prepared by dissolving 25.5 g NaC2H3O2 in a sufficient volume of 0.550 M HC2H3O2 to make 500 ml of the buffer?
Solution:

Amount of C2H5O2- =25.5g NaC2H5O2 x

imol NaC 2 H 3O 2 82.04g NaC 2 H 3O 2

1mol C 2 H 3 O 2 = 0.311molC2H3O21mol NaC 2 H 5 O 2

[C2H3O-]=0.311mol C2H3O2-/0.5 L = 0.622 M C2H3O2Equilibrium calculation:

HC2H3O2 + H2O
Initial conc.

H3O + C2H3O2+

Weak acid Salt: Changes:

Equil conc:

0.55 M --xM (0.55 x) M -xM -+xM + x M (0.662+x) M 0.622 M

Let us assume that x is very small so that (0.55 x) M 0.55 and (0.662+x) M 0.622

[H 3O + ] [C2 H 3O 2 ] (x)(0.622) Ka = = = 1.8 x105 [HC2 H 3O 2 ] 0.55

X = [H3O+] =

0.550 x 1.8 x 10-5 0.622

PH = - log [H3O+] = - log (1.6 x x10-5) = 4.80

10.6

The common ion effect

The repression of the ionization of a weak electrolyte by the presence of a common ion from a strong electrolyte is called the common ion effect. CH3COOH CH3COO- + H+ (weak electrolyte)

When HCl (strong electrolyte) is added to the above solution, H+ become common ion. More [H+] repress the equilibrium to the left (Le Chateliers principle). Therefore the concentration of CH3COOH will increase.
Practice Example:

Determine [H+] and [CH3COO-] in a solution containing 0.1M in both CH3COOH and HCl. (Ka = 1.7 x 10-5)
10.7 The solubility product constant: Ksp

An equilibrium expression between a slightly soluble ionic compound and its ion in a saturated solution is called solubility product. PbCl2(s) Ksp = [Pb2+] [Cl-]2 Pb+(aq) + 2Cl-(aq)

Example:10.9

Calculating the solubility of a slightly soluble solute in the presence of a common ion. What is the molar solubility of PbI2 in 0.10 M KI(aq) ?
Solution:

Equilibrium:

PbI2(s)

Pb2+(aq) + 2I-(aq) 0.10 s s 2s (0.10+2s)

Iinitial conc. M From PbCl2.,M Equil conc.M

Ksp = [Pb2+][ I- ]2 = (s) (0.10 + 2s)2 = 7.1 x 10-9 Let us assume that s is much smaller than 0.10 M, so that 0.10 + 2s 0.10 s (0.10 )2 = 7.1 x 10-9

7.1 x 10 -9 = 7.1 x 10 - 7 M s= 2 (0.10)

Our assumption is well justified: s (7.1 x 10-7) is much smaller than 0.10, and s = molar solubility of PbI2 = 7.1 x 10-7 M.
Example:10.9

Three drops of 0.20 M KI are added to 100.0 ml of 0.010 M Pb (NO3)2. Will a precipitate of lead iodide form ? (Assume 1 drop = 0.05 mL)

PbI2(s)

Pb2+(aq) + 2I-(aq)

Ksp = 7.1 x 10-7

Amount I- = 3 drops x

0.05 ml 1L 0.20 mol KI x x 1 drop 1 000 ml 1L

1 mol I= 3 x 10 5 M x 1 mol KI 3 x 10-5 mol I[I ]= = 3x10-4 M 0.1000L

-

Conc. of Pb (NO3)2 = 0.010 M, so [Pb2+] = 0.01M Ksp = [Pb2+][ I- ]2 = (1 x 10-1) (3 x 10-4)2 = 9 x 10-10 This value is smaller than Ksp (7.1 x 10-9), we conclude that the precipitate of PbI2 will not form.

CHAPTER 11

11.

principle of chemical equilibrium

11.1 Dynamic equilibrium

A condition in which both reactions are still proceeding but the rates of forward and reverse reactions are equal and there is no net change in concentration with time.

CO(g) + 2H2(g)

CH3OHg)

Initially only the forward reaction occurs. As time passes, the forward reaction slows down because of the decreasing concentration of CO and H2. When concentration of CH3OH is sufficiently high, the reverse reaction starts and speeds up to form CO + H2. Eventually two opposite reactions proceed at equal rate, and there is no further change in the net reaction, dynamic equilibrium is said to be established.

11.2 The equilibrium constant expression

The ratio of molar concentration of products and reactant is known as an equilibrium constant.

CO(g) K=

+ 2H2(g)

CH3OH (g)

[CH 3 OH] [CO][H 2 ] 2

General expression for K

aA +bB [C]c [ d ]d KC = [A]a [ b ]b

cC + dD [ ] = molar concentration: mol/L

Example:11.1

The following KC value is given at 298 K for the synthesis of NH3(g) from its elements. N2(g) + 3H2(g) 2NH3(g) KC = 3.6 x 108

What is the value of KC at 298 K for the reaction. NH3(g)

Solution:
1 2

N2(g) +

3 2

H2(g)

KC = ?

For the reverse reaction, the equilibrium constant K =1/KC C 2NH3(g) N2(g) + 3H2(g) K C = 1/3.6x108 = 2.8x10-9

for the following reaction,

NH3(g)

1 2

N2(g) +

3 2

H2(g)

To base the equation on 1 mol NH3(g). we divide all coefficients by 2.Thus, we have to take the square root of K/ C. KC = 2.8 x 10 9 = 5.3 x 10 5

11.3 Equilibria involving gases

aA +bB [C]c [ d ]d KC = [A]a [ b ]b KC =

cC + dD [PC ]c [ PD ]d KP = [PA ]a [ PB ]b

equilibrium constant based on concentration in a gaseous mixture (mole/L) KP= equilibrium constant based on the partial pressures of gases in the gaseous mixture.

According to the ideal gas law, PV = nRT, and so

[ ]= n P = , v RT P P P P [A] = A , [B] = B , [C] = C , [D] = D RT RT RT RT c d P c P d P xP [ ][ ] KC = RT a RT b = Ca D b x RT (c+ d)-(a + b) P P PA x PB [ RT ] [ RT ]
C D A B

n = (c + d) (a + b) = the difference in the stoichiometric coefficients of gaseous mixture.

KC = KP . (RT) n
Example:11.2

For the reaction at 1000 K, formation of SO3(g) , calculate the value of KP. (R = 0.08206 L atm mol-1 K-1)
Solution:

2SO2(g) + O2(g)
ngas = 2 (2 + 1) = -1,

2SO3(g)

(at 1000 K)

KC = KP . (RT) n

= (2.8 x 102) (0.08206 x 1000)-1 = 3.4 11.4 Altering equilibrium conditions (Le Chateliers principle )
When an equilibrium system is subjected to a change in temperature, pressure or concentration of a reacting species, the system reacts in a way that partially offsets the change while reacting a new state of equilibrium.
(or)

When any one of the factors affecting the equilibrium of a chemical system such as temperature, pressure or concentration is changed, the system reacts in such a way as to nullify the effect of change.

Effect of changes in pressure or volume on equilibrium

An increase in external pressure causes a decrease in the reaction volume. When the volume of an equilibrium mixture of gases is reduced, a net reaction occurs in the direction producing a small number of moles of gases. This means the reaction favors the formation of NH3. More NH3 will be produced. N2(g) + 3H2(g) 2NH3(g)

When the gaseous mixture is transferred to the larger flask, the partial pressure of each gas and total pressure drop. Equilibrium shift to an increase volume or produce a large number of moles of gas. This means that NH3 decomposes back to N2 and H2.
Changes in system volume or pressure have no effect in the following equilibrium.

H2 + I2

2HI

CO + H2O

CO2 + H2

There is the same number of moles of reactant and product. There will be no effect of pressure on the equilibrium.

Effect of temperature on equilibrium

Raising the temperature of an equilibrium mixture shifts the forward direction of the endothermic reaction. N2 + O2 2NO
H0 = + 180.5 KJ

Lowering the temperature causes a shift in the forward direction of exothermic reaction. 2SO2 + O2 2SO3
Ho = -180 KJ

The reaction is exothermic reaction. Raising the temperature favors the endothermic reaction, the reverse reaction of the exothermic reaction (that is the decomposition of SO3). Therefore, an equilibrium mixture would have a higher concentration of SO2 and O2at higher temperature.

Effect of a catalyst on equilibrium

A catalyst in a reaction mixture can speed up both the forward and reverse reactions. Equilibrium is reached more rapidly, but the equilibrium amounts are unchanged by the catalyst.
Example:11.3

In the reaction: N2O4(g) 2NO2(g) at 25oC,

the quantities of two gases present in a 3.00 L vessel are 7.64 g N2O4 and 1.56 g NO2. what is the value of KC for the reaction.
Solution:

For both gases, conversion: g

mol

mol/L

7.64 g N 2O 4 x
[N2O4] =

1 mol N 2O 4 92.01g N 2O 4 = 0.0277 M 3.00 L

1.54 g NO 2 x
[NO2] =

1 mol NO 2 46.01g NO 2 = 0.0113 M 3.00 L

[NO 2 ]2 (0.0113) 2 = = 4.61 x 10 -3 KC = [N 2 O 4 ] 0.0277

Example:11.4

When a 0.0200 mol sample of SO3 is introduced into an evacuated 1.52 L vessel at 900 K, 0.00142 mol SO3 is found to be present at equilibrium. What is the value of KP for the decomposition of SO3(g) at 900 K? 2SO3(g)
Solution:

2SO2(g) + O2(g)

KP = ?

The change in amount of SO3 = [SO3]equil [SO3]initially = 0.0142 mol 0.0200 mol = 0.0058 mol SO3 () sign signifies that this amount of SO3 is consumed in equilibrium.

The reaction:
Initial amt:

2SO3(g)
0.0200 mol 0.00 mol

2SO2(g)
0.00 mol

O2(g)
+0.0029 mol

Change:

-0.0058 mol

+0.0058 mol

Eqil. amt:

0.0142mol

0.0058 mol

0.0029 mol

Equi.concentration:

[SO3] equil = 0.0142 mol/1.52 L = 9.34 x 10-3 M [SO2] equil = 0.0058 mol/1.52 L = 3.8 x 10-3 M [O2] equil = 0.0029 mol/1.52 L = 1.9 x 10-3 M

[SO 2 ]2 [O 2 ] [3.8 x 10 -3 ]2 [1.9 x 10 -3 ] KC = = = 3.1 x 10 -4 2 -3 2 [SO 3 ] [9.34 x 10 ] K = K . (RT) n = 3.1 x 10-4 (0.0821 x 900)(2 + 1) - 2
C P

= 2.3 x 10-2

PART TWO

MINISTRY OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF TECHNICAL AND VOCATIONAL EDUCATION

Sample Questions & Worked Out Examples For

E.Ch 01011 ENGINEERING CHEMISTRY

A.G.T.I.(First Year)

Textile & Metallurgy

Chapter ( 1 ) 1. Define the terms: Radioactivity : Radioactivity is a natural phenomenon that is spontaneous emission of radiation by mineral sources. Isotopes : Two or more atoms having the same atomic number but different mass numbers are called isotopes. Atomic mass : fractional mass of fractional mass of Atomic mass of isotope (1) abundance of + isotope (2) abundance of = an element isotope (1) isotope (2) A mole : A mole is the amount of substance that contains of a number of chemical units equal to the number of atoms in exactly 12 g of pure carbon-12. 2. Describe the characteristics of alpha, beta, gamma rays. : Alpha rays are particles carrying two fundamental units of positive charge and having the same mass as helium atom. : Beta rays are negatively charged particles produced by changes occurring within the nuclei of radioactive atoms and have the same properties as electrons. : Gamma rays are electromagnetic radiation of extremely high penetrating power.

Alpha rays Beta rays Gamma rays

3. Write an account for cathode rays. In passing electricity through evacuated glass tubes, a type of radiation emitted by the negative terminal (cathode) that crossed the evacuated tube to the positive terminal (anode). Cathode rays travel in straight line and have properties that are independent of the cathode material Cathode rays are deflected by electric and magnetic fields. Cathode rays are negatively charged fundamental particles of matter found in all atoms and becomes known as electrons. 4. What is the significan features of nuclear atom Most of the mass and all of the positive charge of an atom are centered in a very small region called the nucleus. The atom is mostly empty space. The magnitude of the positive charge is different for different atoms and is approximately one half the atomic weight of the element. There exist as many electrons outside the nucleus as there are units of positive charge on the nucleus. The atom as a whole is electrically neutral.

5. The two isotopes of 6Li and 7Li have masses of 6.01513 and 7.01601 u. The average atomic mass of lithium is 6.941 u. (a) Which of these two isotopes is more abundant? (b) Calculate the percent natural abundance of the two. (a) Lithium (7) is more abundant because the weighted average atomic mass (6.941 u) is much closer to (7) than to(6). (b)The fractional abundance of 6Li isotope= (x) -----------------------------------7Li isotope= (1 x ) fractional mass of fractional mass of Atomic mass of isotope (1) abundance of + isotope (2) abundance of = an element isotope (1) isotope (2) Atomic mass of Li = [ (x) 6.01513.u ] + [ ( 1 x ) 7.01601 u] 6.941 u = 6.01513 x + 7.01601 7.01601 x x = 0.074944 The % abundance. of 6Li isotope The % abundance. of 7Li isotope 6. = 0.074944 x 100% = 7,4944% = ( 100 - 0.074944 ) 100% = 92.5056 %

The percent abundance of 40K atom is 0.012%. How many 40K atom do you ingest by drinking one cup of milk containing 371 mg of K? (K = 39.098 ) 371 10 3 g K 1 mol K 39.0983 g K

(?) 40K atoms =

6.022 10 23 atom K 0.012 atom 40 K 1 mol K 100 atom K

40

= 6.8570 1017 atom 7.

What is the mass, in gram, corresponding to 1.000 u.? 12 g 12 C 1 atom 12 C 1 mol 12 C (?) g = 1 u 12 u 6.02 10 23 12 C atoms 1 mol 12 C = 1.6605 10-24 g

3 8. For the nulide 133 Cs , express the percentage, by number of the fundamental 55 particles in the nucleus that are neutrons. Total particles in the nucleus = 133 No: of neutron in the nucleus = 133 55 = 78 78 ( % )neutrons in the nucleus = 100 % = 67% 133 ****************

Chapter ( 2 ) 1. What is meant by the following terms: Electromagnetic radiation: Electromagnetic radiation is a form of energy transmission through a vacuum or medium in which electric and magnetic fields are propagated as wave. Atomic Spectra : The spectra produced by certain gaseous substances consist of only a limited number of colored lines with dark spaces between them. These discontinuous spectra are called atomic spectra Stationary States stationary states. : The electron has only a fixed set of allowed orbits, called

Pauli Exclusion Principle : No two electrons in an atom may have all four quantum numbers alike. Hunds rule : When orbitals of identical energy are available, electrons initially occupy these orbitals singly. 2. How many quantum numbers are required to specify an electron in a single orbital and what are the values? The four sets of quantum numbers. (i) Principle Q.no. (n) (ii) Orbital Q.no. (l) (iii) Magnetic Q.no. (m1) (iv) Spin Q.no. (n) n = 1, 2, 3, n l = 0, 1, 2, .(n-1) (ml)= + l 0 .-l 1 1 ms = + , 2 2

4 3. What type of orbital (c) n = 5, l = 0 ? n = 2, n = 4, n = 5, is designated (a) n = 2, l = 1, (b) n = 4, l = 2. l=1 l=2 l=0 2p 4d 5s

4. Calculate the energy emitted by the light of a sodium vapor lamp which has wavelength of 589 nm. (h = planks constant = 6.626 10-34 J s, c = 2.998 108 ms-1) = 589 nm = 589 10-9 m hc 6.626 10 34 Js photon 1 2.998 10 8 ms 1 E= = 589 10 9 m = 3.3748 10-19 J / photon 5. How long does it take light from the sun 93 million miles away to the earth? c = 2.998 108 ms-1, ( 1 mile = 1.60931 km ) 93 million miles = 93 106 miles. 1.60931 km 10 3 m 1s (?) second = 93 106 miles 1 mile 1 km 2.988 10 8 m = 499.2189 s 6. Calculate the velocity of a beam of photon moving with a wavelength of 10pm. mass of proton = 1.67 10-24 g, h = planks constant = 6.626 10-34 kg m2 s-1 ) = 10 pm = 10 10-12 m m =1.67 10-24 g = 1.67 10-27 kg = h mv

6.626 10 34 kg m 2 s 1 h = m 1.67 10 27 kg 10 10 12 m v = 3.9676 104 m s-1 v= 7. Calculate the wavelength of an alpha particles if its velocity is 1.5 107 m s-1. Avogadros no, = 6.02 1023, c = 2.998 108 ms-1, h = 6.626 10-34 kg m2s-1, ( alpha particles = 24 He2+ ) particle = He 2+
2 4

molar mass of He =

4 g/mol

5 1 mol 4g 1 mol 6.022 10 23 particles = 6.6423 10-24 g / particles

(?) g of one particle =

m = 6.6423 10-24 g = 6.6423 10-27 kg = 6.626 10 34 kg m 2 s 1 h = = 6.65 10 15 m 27 7 1 mv 6.6423 10 kg 1.5 10 ms = 6.65 10-6 nm

8. The ionization energy of Na is 496 kJ mol-1. What is the wavelength of a photon that will cause this ionization?

496 10 3 J 1 mol = 82.3646 10 20 J / photon 1 mol 6.023 10 23 photons c E =h hc 6.626 10 34 Js 2.998 10 8 ms 1 = = E 82.3646 10 20 J = 2.4118 10-7 m = 241.18 nm E= 9. Describe four sets of quantum numbers for a last added electron of the following elements. State whether they are paramagnetic or diamagnetic. 19K , 32Ge, 16S, 12Mg m l ml ms 1 + K = [ Ar ] 4s1 4 0 0 19 2 1 2 10 + 4p2 4 1 0 32 Ge = [ Ar ] 4s 3d 2 1 2 4 3 1 -1 2 16S = [ Ne ] 3s 3p 1 2 3 0 0 12Mg = [ Ne] 3s 2
*************

6 Chapter ( 3 ) 1. (a) Define the term ionization energy. (b) Are these any atoms for which the second ionization energy is larger than the first? Explain. (a) (b) The ionization energy is the quantity of energy a gaseous atom must absorb so that an electron is stripped from the neutral atom. Na (g) Na+(g) + eSecond ionization energy is always greater than the first ionization energy, because the electron must be removed from a positively charged ions. The attraction between the positive ion and the electron is stronger than between the neutral atom and the electron.

2.

Compare the elements K and Ca with respect to the following properties, (a) Electron configuration (b) Most common ionic charge (c) First ionization energy (d) Atomic radius. K Ca (a) 1s2, 2s2, 2p6, 3s2, 3p6, 4s1 1s2, 2s2, 2p6, 3s2, 3p6, 4s2 (b) +1 +2 (c) K < Ca (d) K > Ca Arrange the following elements in order of inereasing their melting point (a) Na, Si, Al and Mg. (b) CBr4, CCl4, CH4 (a) Na < Mg < Al < Si (b) CH4 < CCl4 < CBr4 The larger the molecular mass, the stronger intermolecular forces, the higher the melting point.

3.

4.

(a) Which one is better reducing agent, Mg or Al? (a) Al has lower ionization energy than Mg and thus is more easily oxidized. Therefore Al is better reducing agent. (b) Which one is better oxidizing agent, Cl or Br? (c) Cl has higher electron affinity than Br and thus is more easily reduced. Therefore Cl is better oxidizing agent. ************

7 Chapter ( 4 ) 1.Explain the terms: Limiting reactant. The reactant that is completely consumed in a reaction is known as limiting reactant. Theoretical yield The calculated quantity of product in a chemical reaction is called theoretical yield of a reaction. Consecutive reaction Reactions that are carried out one after another in sequence to yield a final product are called consecutive reactions. Simultaneous reaction. In simultaneous reactions two or more substances react independently of each other in separate reactions occurring at the same time. Strong electrolyte Strong electrolyte is completely ionized in water solution, and the solution is a good electrical conductor. Weak acid Weak acid Acids that are incompletely (partially) ionized in aqueous solution are called weak acids. Oxidizing agents The substance that causes some other substance to be oxidized and itself reduced. 2. An alloy used in fabricating aircraft structures consist of 93. 7% Al and 6.3% Cu by mass. The alloy has a densily of 2. 85 g cm-3. What volume of the Al-Cu alloy must be dissolved in an excess of HCl(aq) to produce 1 g H2? If one assumes that all the Al, but none of the Cu. reacts with HCl(oq) ( H = 1, Al = 27 ). 2Al(s) + 6HCl(aq) 2AlCl3(aq) + 3H2(g) 1 mol H 2 2 mol Al 27 g Al 100 g alloy 1cm 3 alloy (?) cm alloy = 1gH2 2g H 2 3 mol H 2 1 mol Al 93.7 g Al 2.85 g alloy
3

= 3.3434 cm alloy. 3. If 470.2 L of NH3 gas at STP is used in this reaction and percent yield of urea is 79.4 %. What mass of urea, in gram will be obtained? 2NH3 (g) + CO2 (g) CO(NH2)2 (aq) + H2O(1) (C = 12, O = 16, N = 14, H =1) (?) g Urea = 470.2 LNH3 1mol NH 3 1mol Urea 60 g Urea 22.4 L NH 3 2 mol NH 3 1mol Urea

= 629.73 g Urea (Theoretical yield) Percentage yield = Actual yield = Actual yield 100 % Theoretical yield 629.73 g 79.4 % = 500 g of Urea 100 %

8 4. 34 % by mass HCl,(aq) has a density of 1.025 g/mL. What volume (mL) of this solution would be required to reaSct with 100mL of 0.265 M, AgNO3. (Cl = 35.5, H =1) HCl(aq) + AgNO3(aq) AgCl(s) + HNO3(aq) (?) mL HCl(aq) = 100 10-3 L AgNO3(aq) 0.265 mol AgNO 3 1 mol HCl 1L AgNO 3( aq ) 1 mol AgNO 3

1 mL HCl ( aq ) 36.5 g HCl 100 g HCl ( aq ) = 2.775 mL HCl ( aq ) 1 mol HCl 34 g HCl 1.025 g HCl ( aq ) 5. (a) What volume of solution must be evaporated from 650 mL of 0.0415 M solution to increase the concentration of exactly 0.2 M ? V1 = 650 mL V2 = ? C1 = 0.0415 M C2 = 0.2 M C1 V1 = C1 V1 650 mL 0.0415 M V1 = = 134.88 mL 0.25 M volume of water evaporated = V1 V2 = ( 650 134.88 ) mL = 515.12 mL. (b) What volume of water (mL) must be added to prepare 250 mL of 0.5 M H2SO4 solution from 6M H2SO4 ? V1 = ? C1 = 6M C1 V1 = C2 V2 V1 = 250 mL 0.5 M = 20.83 mL 6M V2 = 250 mL C2 = 0.5 M

volume of water added = V2 V1 = ( 250 - 20.83 ) mL = 229.17 mL. 6. What is percent yield, if the reaction of 30 g P4 and 90 g Cl2 produes 85.6 g PCl3 ? ( P =31, Cl = 35.5 ) P4 (1) + 6Cl2 (g) 4 PCl3 (1)

9 Assuming that P4 is the limiting reagent. (?) mol of PCl 3 = 30 g P4 1 mol P4 4 mol PCl 3 124 g P 4 1 mol P4

= 0.9676 mol PCl3 Assuming that Cl2 is the limiting reagent. (?) mol of PCl 3 = 90 g Cl 2 1 mol Cl 2 4 mol PCl 3 71 g Cl 2 6 mol Cl 2

= 0.8450 mol PCl3 When the smaller amount ( 0.8450 mol ) of PCl3 is formed, Cl2 is completely consumed. Cl2 is limiting reagent. (?) g of PCl3 = 0.8450 mol PCl3 % Yield = 138 g PCl 3 = 116.61 g 1 mol PCl 3

actual yield 100 % theoretical yield 85.6 g = 100% 116.61 g = 73.4 %

7.

(a) VO2+ + MnO4-1 VO+2 ( ans: ) 5VO2+ + MnO4-1 + H2O (b) Cl2 ( ans: ) + OH - Cl- +

+ Mn2+ + H2O 5 VO+2 + Mn2+

(in acid solution) + 2 H+

ClO-3 + H2O

(in base solution)

3 Cl2 + 6 OH - 5 Cl- +

ClO-3 + 3 H2O

8. Write net ionic equation for the following reactions. (a) MgCl2 + NaOH ? Mg2+(aq) + OH-(aq) Mg(OH)2(s) (b) CuSO4 + Na2CO3 ?

10 Cu2+(aq) + CO32-(aq) CuCO3(s) (c) CaCO3 + HCOOH ? CaCO3 (s) + 2 HCOOH(aq) 2 HCOO-(aq) + Ca2+ (aq) + H2O(l) + CO2(g)

9.

The titration of 50 mL. of a saturated solution of sodium oxalate. Na2C2O4 requires 25.8 mL of 0.0214 M, KMnO4. What mass of Na2C2O4, in gram, would be present in 1 L of this saturated solution? ( C = 12, O= 16, Na = 23 )
C 2 O 2- + MnO 4 + H + Mn 2+ + H 2 O + CO 2 (not balance) 4

5 C 2 O 2- + 2 MnO 4 + 16 H + 2 Mn 2+ + 8 H 2 O + 10 CO 2 4

5 mol (?) g Na2C2O4 =

2 mol 25.8 mL KMnO 4 0.0214 mol KMnO 4 5 mol Na 2 C 2 O 4 1000 mLKMnO 4 2 mol KMnO 4 in 50 mL

134 g Na 2 C 2 O 4 = 0.1849 g 1 mol Na 2 C 2 O 4

(?) g /L Na2C2O4 =

0.1849 g 1000 mL = 3. 6992 g / L 50 mL 1L

Chapter ( 5 ) 1. Deseribe any the assumptions of Kinetic molecular Theory of gases. A gas is composed of a very large number of extremely small particles (molecules or atoms) in constant, random, straight-line motion. Molecules of a gas are separated by great distances. The gas is mostly empty space. Molecules collide with one another and with the walls of their container. There are assumed to be no forces between molecules except very briefly during colliding. Individual molecules may gain or lose energy as a result of collisions. In a collision of molecules at constant temperature, however, the total energy remains constant.

11 2. Explain the following terms: (a) diffusion (b) effusion Diffusion is the migration of molecules of different substances as a result of random molecular motion. Effusion is the escape of gas molecules from their container through a tiny hole. 3. A mixture of 4 g of H2 and unknown quantity of He(g) is maintain at STP.

If 10 g of H2 is added to the mixture while conditions are maintained at STP. The volume of the gas is double. What mass of He(g) is present in the mixture? (He = 4. H = 1) Let mol of He (initial) = x mol (?) mol H2 ( initial ) = 4 g H2 x 1mol H 2 = 2 mol H 2 2 g H2 1mol H 2 = 5 mol H 2 2 g H2

(?) mol H2 ( added ) = 10 g H2 x n1 = ( x + 2 ) mol n2 = ( x + 7 ) mol V1 = V V2 = 2 V

By Avogadros theory (V n ) V1 V2 = n1 n 2 ( x + 2) 1 V = ( x+7) 2V x = 3 mol (He) (?) g He = 3 mol He x 4 g He = 12 g He 1 mo He

4. A 1.072 g sample of He(g) is found to occupy a volume of 8.446 L when collected over hexane at 25C and 738.6 mmHg pressure. Determine the vapour pressure of hexane at 25C, in mm Hg. ( He = 4, R = 08205 L atom mol-1 K-1 ). T = 25C + 273 = 298 K M = mRT PV

12 mRT 1.072 g 08205 L atom mol -1 K -1 298 K = = 0.7758 atm PHe = MV 4 g mol 1 8.446 L = 589.6 mmHg Ptotal = PHe + Phexane Phexane = ( 738.6 - 589.6 ) mmHg = 149 mmHg 5. What mass of sodium azide must be dccomposed to produce 1 L of N2(g) at 25C and 751 mmHg? 2NaN3 (s) 2Na (s) + 3N2 (g) 1 atm = 0.9882 atm 760 mm Hg

T = 25C + 273 = 298 K P = 751 mm Hg x PV = nRT n =

0.9882 atm 1 L PV = RT 08205 L atom mol -1 K -1 298 K

= 0.0404 mol N2 (?) Na N 3 = 0.0404 mol N 2 2 mol NaN 3 65 g NaN 3 = 1.75 g 3 mol N 2 1 mol Na N 3

6. The mass of 1.2 L of a gas sample measured at 35C and 754 mm Hg is 2.079 g. What is the root mean square velocity of this gas ? (R = 8.3145 kg m2 s-2 mol-1 K-1 , T = 35 C+ 273 = 308 K P = 754 mm Hg M= 1 atm = 0.9921 atm 760 mm Hg R = 0.08205 L atom mol-1 K-1 ).

mRT 2.079 g 0.08205 L atm mol 1 K 1 308 K = = 44.13 g mol 1 PV 0.9921 atm 1.2 L 3 RT M = 3 8.3145 kg m 2 s -2 mol -1 K -1 308 K = 417.24 ms 1 44.13 g mol 1

U rms =

13 7. Suppose we put a cotton plug saturated with HCl solution into one end of 1 meter tube and simultaneously insert a plug saturated with aqueous NH3 into the other end. How many centimeters from HCl end of the tube will white smoke first form ? ( N = 14, H = 1 , Cl = 35.5 ) Molar mass of NH3 = 17 g / mol Molar mass of HCl = 36.5 g / mol = (100-a ) cm Let, distance from HCl = a cm Distance from NH3

M NH3 dis tan ce from HCl = dis tan ce from NH 3 M HCl a = (100 a ) 17 g mol 1 36.5 g mol 1 = 0.6824

a = 40.56 cm 8. Calculate the pressure exerted by 1 mol of CO2 (g) confined to a volume of 855 cm3 at 30C, Use (a) ideal gas equation and (b) the vander waals equation (c) compare the results and explain. ( a = 3. 5 L2 atom mol-2 ) (a) PV = nRT P= nRT = 29.0 atm V ( vander Waal' s equation ) ( b = 0.0427 L mol-1 )

n2 (b) (P + a ) ( V nb) = n R T V2

n R T n2 a P = V n b V2 P = 25.8 atm (c) The lower pressure calculated by vender Waal's equation is the result of the intermolecular attraction between the real gas molecules. ******

Chapter ( 6 )

14 1. Describe briefly the meaning of: surface tension, normal boiling point, enthalpy of vaporization, the critical point. 2. Equilibrium is established between Br2 (1) and Br2 (g) at 25C. A 250 cm3 sample of the vapor weights 0.486 g. What is the vapor pressure of bromine at 25C, in mmHg? ( Br = 79.9 ) 3. Which of the following molecules can be liquefied at room temperature ( about 25C ) ? O2 ( Tc = 154. 8 K ), CO2 ( Tc = 304.2 K ). SO2 ( Tc = 431K )

4. Cyclohexanol used in the manufacture of nylon, has a vapor pressure of 10 mmHg at 56C and 100 mmHg at 103.7C. Calculate (a) Hvap and (b)normal boiling point. ( R = 8.3145 J mol-1 K-1 ) 5. What are the differences between cohesive forces and adhesive forces?

6. What type of intermolecular attractions are present in each of the following molecules? NH3, Ar, HBr, CH3NH2, Zn, LiBr, CH3OH. 7. 8. What is meant by the terms instantaneous dipole and induced dipole? Which of the following molecules have the higher boiling point? Explain (i) He (or) Ne (ii) n-pentane (or) neo-pentane.

9. Which one of the following substance is a liquid at room temperature? Give explanation. CH3OH, C3H8, N2, CO 10. All electrons in diamond are localized, but that in graphite certain electrons are delocalized. (a) Explain the meaning of localized and delocalized. (b) Which electrons in graphite are delocalized. 11. Which member of each pair is more soluble in CCl4. (Give a brief reason) (i) CH3OH (ii) l2 (iii)NH3 (iv) C6H6 unit cell. (i) CH4 (ii) N2 (or) (or) CH3OH NH3 (or) (or) (or) (or) CHCl3 Hl CH4 C6H4(OH)2

12. Draw the following cubic system and describe the no. of particles (atoms) per

15 (iii)CaCl2 (iv) CH3CH2OH (or) (or) CCl4 CH3OCH3

13. Draw the following cubic system and describe the no. of particles (atoms) per unit cell. (a) Simple cubic (b) Body centered cubic (c) Face-centered cubic 14. 15. K crystallize in a BCC unit cell measuring Ba has a density of 0.533 nm on the edge. What is

the radius of K atom. 3.5 g/cm3 and crystallized in n BCC. Calculate the radius of Ba atom. ( Ba = 137 ) 16. The first order reflection of X-rays of wavelength 0.154nm from a nickel

crystal occurs at an angle of 1240. What is the distance between the plane atoms diffracting this X- ray beam ? 17. Density of lithium is 0.534 g / cm3. The length of unit all measures 0.346 nm on an edge. What is the cubic crystal system occupied by lithium? ( Li = 7 ) 18. (a) What is meant by the term crystal coordination number. (b) Describe the coordination number of following. Mg, Cu, Na 19. 20. Explain the structure of ice crystal lattice and why water is denser than ice. Write an account on liquid crystal.

Chapter ( 7 ) 1. Which of the following compounds are mostly ionic and which are mostly covalent. KH, H2S, SiCl4, Cr2O3 2. (a) Define, Covalent radius, Polar covalent bond.

16 (b) Indicate which of the following bond have the greatest bond length. And shortest bond length. O2, N2, Br2, BrCl 3. Explain why the incomplete octed of BF3 is found generally.

4. Alghough PCl5 is a known compound, NCl5 is not. What reason can you offer for the failure to observe NCl5 ? 5. What is meant by the terms. (i) Valence electron (ii) Resonance Draw the Lewis structure for N2F2, HNO3, SOCl2, F3SN, I3 -, CS2, PF5, XeF4, C2H4 Explain the electron pair repulsion theory with suitable example. Predict the shape of the following molecules and ions. NH-2, BH3, H2O+, IF5, POCl3, SiO4 Calculate the ionic character of H2O. Its dipolement is 1.84 D and bond Discuss the nature of covalent bond in HF molecule by using experimental Percent ionic character of HF molecule is 43%. Its dipolement is = 1.9 D. Estimate the C-H bond energy using a bond energy of 436 kJ mol-1 for H2 and the reaction scheme outlined below. C(g) + 2H2(g) CH4(g) Hrxn = -792 kJ

6. 7. 8. 9. 10.

length is 0.095 nm. 1 D = 3.34 10-30 C.m. ( full ionic charge = 1.6 10-19C) data. ( = 1.91 D, d = 0.092nm ) 11. 12.

13. Enthapy of formation of H2O2 is- 136 kJ mol-1, Estimate the O to O single bond energy. Bond energies for H-H 436 kJ mol-1 O=O 498 kJ mol-1 H-O 464 kJ mol-1 14. Calculate the enthalpy of formation of methanol (CH3OH) CH3OH (g) + H2 (g) Hrxn- ? CH4 (g) + H2O (g) Bond energies C H 414 kJ mol-1 O H 464 kJ mol-1 H H 436 kJ mol-1 C O 360 kJ mol-1 15. Explain the terms. (i) valence band (ii) conduction band

17

16.

How does the electron sea model Explain. ? (i) The deformation of metals? (ii) Electrical conductivity of metals? (iii) Lustrous appearance of metals?

Chapter 8 What mass of H2SO4 is contatned in 25g of 15% by mass solution? What is the molality of 20% by mass of H2SO4? 14.8 M aqueous ammonia solution has a density of 0.898 g/mL. What is XNH3 is this solution. ( N = 14, H = 1 ) 4. What is the molarity of 10 % by mass H2SO4 solution having a density of 1.07 g/ mL? 5. What mass of water must be added to 1 kg of 1.12 m CH3OH (aq:) to reduce the malality to 1.00 m CH3OH(aq:). 6. Define: Henrys Law At 0C and an O2 pressure of 1.00 atm, the aqueous solubility of O2(g) is 48.9 mL O2 per liter. What is the molarity of O2 is a saturated water solution when the O2 is under its nonmal partial pressure in air, 0.2095 atm? 7. Calculate the mole fraction of solute in the following aqueous solution. (C = 12, H = 1, O = 16, N = 14) (a) 13.2 % C2H5 OH by mass (b) 0.512 m urea CO (NH2)2 1. 2. 3.

8. Calculate the vapor pressure of solution at 25C containing 26.9 g of Urea CO(NH2)2 is 712 g H2O. (Vapor pressure of water at 25C is 23.8 mmHg) (N =4, H = 1, O = 16, C = 12) 9. An aqueous solution that is 0.205 m urea is formed to boil at 100.025C. (Kg = 0.512C m4). Is the actual atmospheric pressure above or below 760 mmHg?

10. 1.2 g sample of an unknown covalent compound is dissolved in 50 g of benzene and the solution freezes at 4.92C. Determine molar mass of the compound. ( Kf = 5.12C) 13. An osmotic pressure of 3.56 mmHg is measured for 0.288 g of protein in 25 mL of solution at 25C. What is the molar mass of the protein? Chapter 9

18 1. Identify acid or base for each of the species in the following forward and reverse reactions. (a) H2O + OCl(b) H2PO + NH3 4 HOCl + OHNH + + HPO 2 4 4

2. If 535 ml of gaseous HCl, at 26.5C and 747 mmHg is dissolved in water to prepare 625 mL of solution. What is the pH of this solution. (R = 0.0812 L atm mol-1 K-1) 3. Calcualte the pH of KOH solution that is 3% by mass KOH and has a density of 1.0242 g mL-1. ( K = 39, O = 16, H = 1 ) 4. Calculate the pH of a buffer solution containing. (a) 0.1 M. methanoic acid and 0.01 M sodium methanoate. ( Ka = 1.8 10-5 ) (b) 0.15. acetic acid and 0.5 M CH3COONa. (Ka = 1.7 1 - 5)

What mass of CH3COONa must be dissolved in 0.3L of 0.25 M, CH3COOH to produce a solution pH = 5.1 . (Ka = 1.74 x 10-5 ) ( C = 12, H = 1, O = 16, Na = 23 ) 6. Cocaine (C2H22O4N ) is an alkaloid, that is soluble in water to the extent of 0.17 g / 100 mL. pH of this solution is 10.08. What is the value of Kb for cocaine. 7. The solubiliry of certain metallic hydroxide M(OH)3 is 1.0 x 10-5 mol L-1 Calculate the Ksp of M (OH)3. 8. The solubility of silver carbonate at 25C is 1.1610-1 M. Calculate the solubility product of that compound. 9. Lead (II) iodide saturated solution, its Ksp is 7.1 10-9 at 25C. Calculate the solubility of Pbl2 ?

5.

Chapter 10 1. 0.001 mole of sample of S2 (g) dissociate in 0.5 L flask at 1000K.At equilibrium, 1 10-11 mole S (g) is present. What is Kc and Kp? S2 (g) 2S(g)

2. What is the percent dissociation of N2O4(g) f 1.5 mole of N2O4(g) is introduced into a evacurated 2.5 L vessel at 25C ?

19 N2O4(g) 3. 2NO2(g) Kc = 4.61 10-3. 2C(g) proceed to the

The endothermic reaction A (g) + B (g)

equilibrium condition at 200C. Which of the following statements are true? (a) If the mixture is transferred to a reaction vessel of twice the volume. The concentration of reactants and products will remain unchanged. (b) Addition of B will result in the formation of a greater amount of C(g). (c) Lowering the reaction temperature to 100C will result in the formation of a greater amount of C (g). 4. ! g {C;5 os omtrpdiced omtp a 250 mL tlask and it is heated to 300C, where PCl3(g) + Cl2(g)

the following equilibrium establish. PCls(g)

The quantity of Cl2 present at equilibrium is found to be 0.25g. What is the value of Kc for the dissociation reaction at 300C? (P = 31, Cl = 35.5) 5. Describe the relationship between Kc and Kp.