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GROUP VIIA The Halogens

Halogens (Greek hals, salt; genes, born)

1.Tnh ch t l h c 2.Tnh ch t ha h c 3.i u ch v ng d ng

4.Hidro halogenua 5.H p ch t ch a oxi c a halogen


Department of Inorganic Chemistry - HUT

Group 17 Elements
Also known as Group VIIA Halogens Nonmetals:
Fluorine (F) and Chlorine (Cl) are gases Bromine (Br) is a liquid Iodine (I) is a solid

Metalloid:
Astatine (At) is a solid
Department of Inorganic Chemistry - HUT

Department of Inorganic Chemistry - HUT

2 s

*2 s

2 z

2 x

2 *2 *2 y x y Department of Inorganic Chemistry - HUT

The Lewis dot structure

X
ns2np5

ns2np4nd1: ClF3
ns2np3nd2: BrF5

ns2np2nd3: IF7

Department of Inorganic Chemistry - HUT

Isotopes
Cl-35 makes up about 75% of chlorine atoms in nature, and Cl-37 makes up the remaining 25% the average atomic mass of Cl is 35.45 amu Cl-35 has a mass number = 35, 17 protons and 18 neutrons (35 - 17)
Atomic Symbol A = mass number Z = atomic number

AX Z
35 17

= X-A

Cl

Department of Inorganic Chemistry - HUT

Halogens are fluorine, F; chlorine, Cl; bromine, Br; iodine, I; and astatine, At. Halogens contain 7 valence electrons. As elements, halogens are diatomic. Fluorine is a reactive, pale, yellow gas. F is used in compounds of carbon to form fluorocarbons. Teflon is an example of a fluorocarbon. Other fluorocarbons include the Freons used as refrigerants. Many fluorocarbons are no longer used because of their effect on the ozone layer.

Chlorine is a reactive green-yellow gas.


Cl2 used to purify water and in the production of paper, textiles, bleaches, medicines, and other consumer products.

Bromine is a red liquid


Br is used in photographic chemicals, dyes, pharmaceuticals, and fire retardants.

Iodine is a crystalline solid.


I2 sublimes, turns directly from a solid to a gas when heated. Iodine is present in brine fields in oil field in California and Louisiana and in sea plants. Iodine compounds are used in photographic chemicals and medicines. Iodine is required by the human body in the thyroid.

All isotopes of astatine are radioactive.

Cation formation vacates outermost orbital and decreases e-e repulsions SIZE DECREASES

Ionic radii

Anion formation increases e-e repulsions so they spread out more SIZE INCREASES

**

GROUP VIIA The Halogens

1.Tnh ch t l h c 2.Tnh ch t ha h c 3.i u ch v ng d ng

4.Hidro halogenua 5.H p ch t ch a oxi c a halogen


Department of Inorganic Chemistry - HUT

Tnh oxi ha m nh nh t

X2(k) = 2X(k) X-X

Tnh kh

Department of Inorganic Chemistry - HUT

Phn t

EA-A [kJ/mol] 105 72 49 45 43 F2 Cl2 Br2 I2 At2 151 239 190 149 --

di LK [] 2.67 3.08 3.92 --1.42 1.99 2.28 2.67 --

F khng c orbital ha tr d tham gia lin k t


Orbital ha tr tng d n cc: Nng l ng S l ng t chnh: n

Li2 Na2 K2 Rb2 CS2

S nt hm xuyn tm: n-l-1

Phn t p EA-A [kJ/mol] lA-A []

Li2 1 105 2.67

Be2 0 0 --

B2 1 289 1.59

C2 2 628 1.31

N2 3 941 1.10

O2 2 494 1.21

F2 1 151 1.42

Ne2 0 0 --

Nng l ng lin k t c ng ha tr Echt

xen ph c a cc orbital ha tr l n khi: - Mi n xen ph r ng v m t e mi n xen ph l n. - Z i v i orbital ha t l n. - S l ng t chnh n nh . - Hi u nng l ng cc orbital ha tr trong nguyn t v gi a cc nguyn t tham gia lin k t l nh . - S nt hm xuyn tm c a c a orbital ha tr l t (s nt = n l -1). - mi n xen ph c nhi u orbital ha tr tham gia. Y u t quy t nh nng l ng lin k t l b c lin k t. Khi b c lin k t b ng nhau nhng Echt khc nhau l do xen ph cc orbital ha tr l khc nhau. Trong 1 chu k, t tri qua ph i: - Z i v i cc orbital ha tr tng d n Echt tng d n. - Hi u nng l ng cc orbital ha tr , Enp-Ens, gi m d n Echt gi m d n T ng Echt s l gi tr c nh tranh gi a 2 xu h ng ny. Trong 1 phn nhm A, t trn xu ng: - Nng l ng cc orbital ha tr cng d ng tng d n. - S l ng t chnh n c a cc orbital ha tr tng lm s nt hm xuyn tm tng. Echt gi m d n. Department of Inorganic Chemistry - HUT

F2

2 F2 + SiO2 SiF4 + O2 nF2 + 2 Xe 2 XeFn ( Kr , Xe, Rn; n = 2, 4, 6)

F2 + H 2 2 HF 0 H =268.6 kJ / mol
thap ,bongtoi
298,s

no o t 0

2 F2 + H 2O 4 HF + O2
thuong

t0

Nng l ng lin k t F-F nh i l c v i electron l n Nng l ng lin k t c a F v i nguyn t khc l n n Kh nng hidrat ha c a ion F- l Department of Inorganic Chemistry - HUT

X2
HF
H0298,s [kJ/mol] -268.6

X 2 + H 2 2 HX

0 298,s

HCl
-92.31

HBr
-36.23

HI
25.9 B t u 2000C, l ph n ng thu n ngh ch

c i m N nhi t th p v trong t i

N khi un nng B t u ho c nh sng 2000C, trn t ngo i 7000C c ph n ng ngh ch

Department of Inorganic Chemistry - HUT

X2
0
[V]

nguoi Cl2 + 2 KOH KClO + KCl + H 2O

3Cl2 + 6 KOH KClO3 + 5 KCl + 3H 2O


100o C

F2/F-

Cl2/Cl-

Br2/Br-

I2/I-

2.87

1.36

1.07

0.54

Cl2 + 2 Br 2Cl + Br2

Tnh kh

Br2 + 2 I 2 Br + I 2 Cl2 + 2 I 2Cl + I 2


nau Iot bien mat

Cl2 + I 2 + 6 H 2O 2 HIO3 + 10 HCl


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X2

Department of Inorganic Chemistry - HUT

GROUP VIIA The Halogens

1.Tnh ch t l h c 2.Tnh ch t ha h c 3.i u ch v ng d ng

4.Hidro halogenua 5.H p ch t ch a oxi c a halogen


Department of Inorganic Chemistry - HUT

F2

Fluorine (Latin fluo, flow), symbol F, chemically reactive, poisonous gaseous element. The atomic number of fluorine is 9.

Fluorine occurs naturally in the combined form as

fluorite-CaF2, cryoliteNa3AlF6, and apatiteCa5(PO4)3F. Fluorite, from which most fluorine

1886

compounds are generally derived, is commonly mined in the United States from large deposits in northern French chemist Kentucky and southern Illinois. Fluorine also occurs as fluorides in seawater, rivers, and mineral springs, in the stems of certain grasses, and in the bones and teeth of Henri Moissan. animals. It is the 17th element in order of abundance in the crust of the earth. Department of Inorganic Chemistry - HUT

CaF2

FLUORITE, "The Most Colorful Mineral in the World"

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Na3AlF6
Cryolite
, mineral, sodium aluminum fluoride (Na3AlF6). Cryolite has a hardness of 2.5 and a specific gravity of about 3. It crystallizes in the monoclinic system (see Crystal). It is colorless and ranges from transparent to translucent. It has a waxy appearance, making it almost invisible when powdered and suspended in water. Cryolite was found in abundance only at Ivigut, Greenland. However, that deposit has been exhausted since 1987. The mineral is still found in small quantities in Colorado, USA; Sallent, Huesca Province, Spain; Miask, Urals, USSR; and Montreal, Quebec, Canada. It is used chiefly as a solvent of alumina in the electrolytic preparation of aluminum. Because of its scarcity, this mineral has been replaced in industrial processes by artificially produced sodium aluminum fluoride.
Department of Inorganic Chemistry - HUT

Ca5(PO4)F
Apatite
(Greek apate, deception), mineral so named because it resembles various other minerals for which it might be mistaken. It consists chiefly of phosphate of lime. Apatite is a distinct mineral of composition Ca5(PO4)3F in which some or all of the fluorine may be replaced by chlorine (chlorapatite). The mineral crystallizes in the hexagonal system (see Crystal) and has a hardness of 5 and a specific gravity of 3.2. When pure, apatite is colorless and transparent, but it may exhibit various degrees of color and opacity. These mineral phosphates of lime were often used in the preparation of fertilizers, but they have been replaced by phosphate rock.
Department of Inorganic Chemistry - HUT

F2

The preparation of fluorine as a free element is difficult and seldom done, since free fluorine is very reactive. However, gaseous fluorine

can be prepared by

electrolytic

techniques (KHF2, HF 100 0C


, and liquid fluorine may be prepared by passing

the gas through a metal or rubber tube surrounded by liquid air.


Department of Inorganic Chemistry - HUT

Fluorine compounds have many applications. The chlorofluorocarbons, odorless and nonpoisonous liquids or gases such as

Freon-CFCl3, are used as a

dispersing agent in aerosol sprays and as a refrigerant. In 1974, however, some scientists suggested that these chemicals reached the stratosphere and were destroying the earth's ozone layer. With confirmation of these findings by the late 1980s, the production of these chemicals began to be phased out (see Environment). Another chemical,

Teflon, a fluorine plastic that is very resistant to most chemical action,

is widely used to make such products as motor gaskets and dashboard accessories in the automobile industry. Teflon is also used as a coating on the inner surface of frying pans and other kitchen utensils to reduce the need for fat in cooking. Many organic fluorine compounds developed during World War II (1939-1945) showed extensive commercial potential. For example, the liquid fluorinated hydrocarbons derived from

lubricating oils. Uranium hexafluoride, the only volatile compound of uranium, is used in the gaseous diffusion process to provide fuel for atomic power plants
petroleum are useful as highly stable
Department of Inorganic Chemistry - HUT

CARNALLITE

Cl2

Chlorine, symbol Cl, greenish-yellow gaseous element. In group 17 (or VIIa) of the periodic table, chlorine is one of the halogens. The atomic number of chlorine is 17.

Elementary chlorine was first isolated in 1774 by the Swedish chemist Carl Wilhelm Scheele, who thought that the gas was a compound; it was not until 1810 that the

British chemist Sir Humphry Davy proved


that chlorine was an element and gave it its present name.

KMgCl3 - 6H2O, Hydrated Potassium Magnesium Chloride Department of Inorganic Chemistry - HUT

HALITE KCl, Potassium Chloride NaCl, Sodium Chloride

dienphan 2 NaCl + 2 H 2O 2 NaOH + Cl2 Z + H 2 Z comangngan

dunnhe 4 HCl + MnO2 2 H 2O + MnCl2 + Cl2 Z


The gas has an irritating odor and in large concentration is dangerous; it was the first substance used as a poison gas in World War I (1914-1919) (see Chemical and Biological Warfare). Department of Inorganic Chemistry - HUT

Most chlorine is produced by the electrolysis of ordinary salt solution, with sodium hydroxide as a by-product. Because the demand for chlorine exceeds that for sodium hydroxide, some industrial chlorine is produced by treating salt with nitrogen oxides or by oxidizing hydrogen chloride. Chlorine is shipped as a liquid in steel bottles or tank cars. It is used for bleaching paper pulp and other organic materials, destroying germ life in water, and preparing bromine, tetraethyl lead, and other important products.

Department of Inorganic Chemistry - HUT

Br2
Cl2 + 2 Br 2Cl + Br2 Z
Bromine has been used in the preparation of certain dyes and of dibromoethane (commonly, ethylene bromide), a constituent of antiknock fluid for leaded gasoline. Bromides are used in photographic compounds and in natural gas and oil production.

Department of Inorganic Chemistry - HUT

I2
3

Thyroid Gland, endocrine gland found in almost all vertebrate animals and so called because it is located in front of and on each side of the thyroid cartilage of the larynx. It secretes a hormone that controls metabolism and growth.

2 IO + 5 HSO 3HSO4 + 2 SO4 + H 2O + I 2

Iodine is medicinally very important because it is an essential trace element, present in a hormone of the thyroid gland that is involved in growth-controlling and other metabolic functions. Without iodine, stunted growth and conditions such as goiter can result. Thus in result areas where iodine is not sufficiently abundant naturally, iodine-containing salt serves to make up the deficit. In medicine, iodine-alcohol solutions and iodine complexes have been used as antiseptics and disinfectants. Radioisotopes of iodine are used in medical and other fields of research. More broadly, various iodine compounds find use in photography, the making of dyes, and cloud-seeding operations. In chemistry, various iodine compounds serve as strong oxidizing agents, among other2uses.

At2

Astatine (Greek astatos, unstable), symbol At, radioactive element that is the heaviest of the halogens. The atomic number of astatine is 85. Originally called alabamine because of early research with the element at Alabama Polytechnic Institute, it was prepared in 1940 by bombarding bismuth with highenergy alpha particles. The first isotope synthesized had an atomic weight of 211 and a half-life of 7.2 hours. Subsequently, astatine-210 was produced and found to have a half-life of about 8.3 hours. Isotopes of astatine with mass numbers from 200 to 219 have been cataloged, some with half-lives measured in fractions of a second. Astatine is the halogen that behaves most like a metal and that has only radioactive isotopes. It is highly carcinogenic: Mammary and pituitary tumors have been induced in laboratory animals by a single injection.
Department of Inorganic Chemistry - HUT

GROUP VIIA The Halogens

1.Tnh ch t l h c 2.Tnh ch t ha h c 3.i u ch v ng d ng

4.Hidro halogenua 5.H p ch t ch a oxi c a halogen


Department of Inorganic Chemistry - HUT

HX
G
0 hHX

H X .a q
G

G 0

.a q +
G
0 h

X
H+

.a q
G
0 h
X

HX (k ) + aq H (k ) + X (k ) + aq H + (k ) + X (k ) + aq

0 LK

G G

0 IH

0 AX

0 0 0 0 0 G 0 = GhHX + GLK + GI0H + GAX + Gh + + Gh

H X Department of Inorganic Chemistry - HUT

HF
EH-X [kJ/mol]
0 GhHX

HCl
431 -4.2 404.5 1320.2 -366.8 -1393.4 -39.7

HBr
364 -4.2 339.1 1320.2 -345.4 -1363.7 -54.0
K = 7.2104

HI
297 -4.2 272.2 1320.2 -315.3 -1330.2 -57.3

565

0 GLK

GI0H
0 GAX
0 Gh +
H

0 Gh
X

G 0

23.9 535.1 1320.2 -347.5 -1513.6 18.1

F + H 3O + HF + H 2O

HF l axt y u

K =5.1 HF2 F + HF H bonding

HCl, HBr, HI l cc axit m nh

Department of Inorganic Chemistry - HUT

16HCl + KMnO4 5Cl2 Z +2MnCl2 + 2KCl + 8H2O 2HBr + H2 SO4 SO2 + Br2 + 2H2O 8HI + H2 SO4 H2 S + 4I 2 + 4H2O 2HI + 2FeCl3 2FeCl2 + I 2 + 2HO

Tr HF, tnh kh tng d n HCl, HBr, HI Tr HF, tnh kh tng d n HCl, HBr, HI

4HF + SiO2 SiF4 + 2H2O 6HF + SiO2 H2 [ SiF6 ] + 2H2O


Department of Inorganic Chemistry - HUT

2HF + SiF4 H2 [ SiF6 ]

Hydrogen Chloride, colorless, corrosive, nonflammable gas, formula HCl, with a characteristic penetrating,
suffocating odor. It melts at - 114.22 C, boils at - 85.05 C, and has a density of 1.268 (air = 1.000). Hydrogen chloride dissolves readily in water: 1 vol. of water at 20 C absorbs 442 vol. of hydrogen chloride gas at atmospheric pressure. The resulting solutionhydrochloric acidcontains 40.3 percent hydrogen chloride by mass and has a specific gravity of 1.20. This solution fumes strongly in moist air, but dilution stops the fuming. Hydrogen chloride becomes less soluble in water as the water temperature rises, and it is less soluble in alcohol, ether, and in other organic liquids. In solution in water, the molecules of hydrogen chloride ionize, becoming positively charged hydrogen ions and negatively charged chloride ions. Because it ionizes easily, hydrochloric acid is a good conductor of electricity. The hydrogen ions give hydrochloric acid its acidic properties, so that all solutions of hydrogen chloride and water have a sour taste; corrode active metals, forming metal chlorides and hydrogen; turn litmus red; neutralize alkalies; and react with salts of weak acids, forming chlorides and the weak acids. Hydrogen chloride is produced industrially as a by-product of the reaction of chlorine with hydrocarbons to produce organic chlorides. Hydrochloric acid may be made by the reaction of sodium chloride with sulfuric acid or by combining hydrogen and chlorine. Crude industrial hydrochloric acid is called muriatic acid. It is used in large quantities in the preparation of chlorides and for cleaning metals and in industrial processes such as preparation of corn syrup and glucose from cornstarch. Small amounts of hydrochloric acid are secreted by cells in the lining of the stomach to aid in food digestion.

Hydrobromic acid is a solution of hydrogen bromide gas, formula HBr, and water. The gas is colorless, with
a penetrating odor, boiling point - 67 C. Hydrobromic acid is formed by the direct union of hydrogen and bromine in the presence of a catalyst, such as platinum; another method is to brominate phosphorus to form phosphorus tribromide, which hydrolyzes in water to form phosphorous acid and hydrobromic acid (see Hydrolysis). Hydrobromic acid, like hydrochloric acid, is a strong acid. It reacts with metals, some salts, and bases to form bromides.

Hydriodic acid is a solution of hydrogen iodide gas and water, with the formula HI. The gas is colorless, with
a penetrating odor, boiling point -35 C. Hydriodic acid is formed in the same manner as hydrobromic acid. It is less stable than any of the other acids described above, and it decomposes readily into iodine and hydrogen. Hydriodic acid is often used as a reducing agent.

HF HCl HX

CaF2 + H2 SO4 (dac) CaSO4 + 2HF

RH + Cl2 RCl + HCl H2 + Cl2 2HCl


burn

PX 3 + 3HOH H3 PO3 + 3HX


Department of Inorganic Chemistry - HUT

X = Br , I

GROUP VIIA The Halogens

1.Tnh ch t l h c 2.Tnh ch t ha h c 3.i u ch v ng d ng

4.Hidro halogenua 5.H p ch t ch a oxi c a halogen


Department of Inorganic Chemistry - HUT

Covalent Oxides
F2O, Cl2O and Cl2O7
Cc h p ch t ny u khng b n v t c ng d ng trong th c t

F2O(g) + H2O(l) 2HF(aq) + O2(g) Cl2O(g) + H2O(l) 2HOCl(aq) Cl2O7(l) + H2O(l) 2HClO4(aq) O Cl O O Cl O O O O Cl O Cl2O7(s) + O Cl O O O -

O O Cl2O7(g)/(l)

NAMING OXOANIONS - EXAMPLES


Prefixes per Root Suffixes ate Chlorine Bromine Iodine

perchlorate perbromate periodate [ ClO4-] [ BrO4-] [ IO4-]


No. of O atoms

ate

chlorate [ ClO3-] chlorite [ ClO2-]

bromate [BrO3-] bromite [ BrO2-]

iodate [ IO3-] iodite [ IO2-]

ite

hypo

ite

hypochlorite hypobromite hypoiodite [ ClO -] [ BrO -] [ IO -]

Axit Hipocloro Km b n N c Javen

HOCl KClO3
Cl2 + HOH HCl + HOCl
anh sang mat troi xuc tac, chat khu

CaOCl2

Kali clorat Thu c n

2 HOCl 2 HCl + O2
CaCl2 2HOCl H 2O + Cl2O chat hut nuoc

3HOCl 2 HCl + Department of Inorganic Chemistry - HUT HClO3


dun nong, de xay ra

HOCl
Hipoclorit N c Javen

Cl2 + HOH HCl + HOCl

+2NaOH

NaCl + NaOCl + 2 H 2O

Cl2 + 2 NaOH ( nguoi)

i n phn khng mng ngn dung d ch ngu i NaCl


Department of Inorganic Chemistry - HUT

CaOCl2
Cl Cl2 + Ca (OH ) 2 Ca OCl
HOCl c tnh ch t oxi ha m nh nn n c Javen v CaOCl2 ng d ng t y tr ng v t y u
Department of Inorganic Chemistry - HUT

+ H 2O

KClO3
3Cl2 + 6OH (nong )
i n phn khng mng ngn dung d ch KCl nng

Axit cloric ch t n t i trong dung d ch khng qu 50 %, l axit m nh, ch t oxi ha m nh

3HOCl 2 HCl + HClO3


dun nong, de xay ra

80 0C

5Cl + ClO + 3H 2O

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ch t oxi ha m nh

ClO + 5Cl + 6 H 3Cl2 Z +3H 2O ClO + 6 I + 6 H Cl + 3I 2 + 3H 2O


Ion clorat oxi ha Cl-, Br-, I- trong mi tr ng axit Khng x y ra trong mi tr ng trung tnh, ki m
3 +

P, S, C

2 KClO3 (r ) 2 KCl + 3O2 Z


MnO2 250o C

Ngi n Pho hoa Dim (50 % l KClO3)

4KClO3 (r) 4KClO4 + KCl


nhietkocao

Axit pecloric l axit m nh nh t trong cc axit


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Inorganic compounds are substances not considered to be derived from hydrocarbons The rules for naming, or nomenclature, of simple inorganic compound is covered now (organic nomenclature is covered later) Binary compounds are compounds comprised of two different elements The goal is to be able to convert between the chemical formula and the name

The first element in the formula is identified by its English name, the second by appending the suffix ide to its stem (eg. compound AB)
Chemical Symbol O S N P F Cl Br I Name as Name as Stem First Element (A) Second Element (B) oxoxygen oxide sulfsulfur sulfide nitrnitrogen nitride phosph- phosphorus phosphide fluorfluorine fluoride chlorchlorine chloride brombromine bromide iodiodine iodide

The number of each type of atom is specified with Greek prefixes


Greek Prefixes mono= 1 (often omitted) di=2 tri=3 tetra=4 penta=5 Examples: PF5 = phosphorus pentafluoride HCl = hydrogen chloride N2O5 = dinitrogen tetraoxide hexaheptaoctanonadeca=6 =7 =8 =9 = 10

Note: many compounds have common names, like water for H2O.