slide 1 group viia the halogens halogens greek hals “salt” genes “born” tính chất lý học tính chất hóa học điều chế và ứng dụng hidro halogenua hợp chất chứa oxi của halogen department of inorgan

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 [r]

(1)

GROUP VIIA The Halogens

Halogens (Greek hals, “salt”; genes, “born”)

1.Tính chất lý học 2.Tính chất hóa học

3.Điều chế ứng dụng 4.Hidro halogenua

5.Hợp chất chứa oxi halogen

(2)

Department of Inorganic Chemistry - HUT

Group 17 Elements Also known as Group VIIA

Halogens

Nonmetals: Nonmetals:

Fluorine (F) and Chlorine (Cl) are gases

Bromine (Br) is a liquid

Iodine (I) is a solid Metalloid:

Metalloid:

(3)

(4)

2 *2 2 2 2 *2 *2

s s z x y x y

(5)

The Lewis dot structure

X nsns22npnp44ndnd11: : ClFClF

3

ns

ns22npnp55 nsns22npnp33ndnd22: : BrFBrF 5

5

ns

ns22npnp22ndnd33:: IF IF 7

7  

    

    

    

     

 

(6)

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 = X-A

Cl

35

17

(7)

• Halogens are fluorine, F; chlorine, Cl; bromine, Br; iodine, I; and astatine, Halogens are fluorine, F; chlorine, Cl; bromine, Br; iodine, I; and astatine, At.

At.

• Halogens contain valence electrons.Halogens contain valence electrons.

• As elements, halogens are diatomic.As elements, halogens are diatomic.

• Fluorine is a reactive, pale, yellow gas.Fluorine is a reactive, pale, yellow gas.

• F is used in compounds of carbon to form fluorocarbons F is used in compounds of carbon to form fluorocarbons

– Teflon is an example of a fluorocarbon.Teflon is an example of a fluorocarbon.

– Other fluorocarbons include the Freons used as refrigerants.Other fluorocarbons include the Freons used as refrigerants.

– Many fluorocarbons are no longer used because of their effect on the Many fluorocarbons are no longer used because of their effect on the ozone layer.

(8)

• Chlorine is a reactive green-yellow gas.Chlorine is a reactive green-yellow gas.

– ClCl22 used to purify water and in the used to purify water and in the production of paper, textiles, bleaches,

production of paper, textiles, bleaches,

medicines, and other consumer products.

• Bromine is a red liquidBromine is a red liquid

– Br is used in photographic chemicals, Br is used in photographic chemicals,

dyes, pharmaceuticals, and fire retardants

(9)

• Iodine is a crystalline solid.Iodine is a crystalline solid.

– II22 sublimes, turns directly from a solid to a gas sublimes, turns directly from a solid to a gas

when heated.

– Iodine is present in brine fields in oil field in Iodine is present in brine fields in oil field in

California and Louisiana and in sea plants.

– Iodine compounds are used in photographic Iodine compounds are used in photographic

chemicals and medicines.

– Iodine is required by the human body in the thyroid.Iodine is required by the human body in the thyroid.

(10)

Ionic radii

Cation formation vacates outermost orbital and decreases e-e repulsions

SIZE DECREASES

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

SIZE INCREASES

(11)

1.Tính chất lý học

2.Tính chất hóa học

(12)

Tính oxi hóa mạnh nhất

Tính khử

X2(k) = 2X(k)

X-X

A

(13)

Phân tử EA-A [kJ/mol]

Độ dài LK [Å] Li2 Na2 K2 Rb2 CS2 F2 Cl2 Br2 I2 At2 105 72 49 45 43 151 239 190 149 2.67 3.08 3.92 1.42 1.99 2.28 2.67

F khơng có orbital hóa trị d tham gia liên kết

Phân tử Li2 Be2 B2 C2 N2 O2 F2 Ne2

p

EA-A [kJ/mol] lA-A [Å]

1 105 2.67 0 289 1.59 628 1.31 941 1.10 494 1.21 151 1.42 0

Orbital hóa trị tăng dần các:

Năng lượng

Số lượng tử chính: n

(14)

Năng lượng liên kết cộng hóa trị Echt

Độ xen phủ orbital hóa trị lớn khi:

- Miền xen phủ rộng mật độ e miền xen phủ lớn - Z’ orbital hóa tị lớn

- Số lượng tử n nhỏ

- Hiệu lượng orbital hóa trị nguyên tử nguyên tử tham gia liên kết nhỏ

- Số nút hàm xuyên tâm của orbital hóa trị (số nút = n – l -1) - Ở miền xen phủ có nhiều orbital hóa trị tham gia

Yếu tố định lượng liên kết bậc liên kết Khi bậc liên kết nhau Echt khác độ xen phủ orbital hóa trị khác nhau.

Trong chu kỳ, từ trái qua phải:

- Z’ orbital hóa trị tăng dần  Echt tăng dần

- Hiệu lượng orbital hóa trị, Enp-Ens, giảm dần  Echt giảm dần Tổng Echt giá trị cạnh tranh xu hướng

Trong phân nhóm A, từ xuống:

- Năng lượng orbital hóa trị dạng tăng dần.Năng lượng orbital hóa trị dạng tăng dần.

- Số lượng tử n orbital hóa trị tăng làm số nút hàm xuyên Số lượng tử n orbital hóa trị tăng làm số nút hàm xuyên

tâm tăng.



(15)

F

F222

2

2 2 n ( , , ; 2, 4,6)

F SiO SiF O

nF Xe XeF Kr Xe Rn n

   

   

0

298,

,

2 2 268.6 / 2

s

no o t thap bongtoi H kJ mol

F H HF

 

       

0

2 2 2

2F  H O    t thuong 4HF O

Năng lượng liên kết F-F nhỏ

Ái lực với electron lớn

Năng lượng liên kết F với nguyên tố khác lớn

Khả hidrat hóa ion F

(16)

2 2 2

X  H   HX

X

X22

HF

HF HClHCl HBrHBr HIHI

ΔH0 298,s

[kJ/mol]

-268.6 -92.31 -36.23 25.9

Đặc điểm Nổ nhiệt độ thấp trong tối

Nổ đun nóng hoặc ánh sáng tử ngoại

Bắt đầu 2000C,

7000C có phản

ứng nghịch

Bắt đầu 2000C,

phản ứng thuận nghịch

0 298,s H

(17)

Tính khử

X

X22 2

100

2

3 6 o 5 3

nguoi

C

Cl KOH KClO KCl H O

Cl KOH KClO KCl H O

     

F

F22/F/F-- ClCl 2

2/Cl/Cl-- BrBr22/Br/Br-- II22/I/I-

-ε

ε00 [V] 2.872.87 1.361.36 1.071.07 0.540.54

2 2 2 2 2 2 2 2 2

Cl Br Cl Br

Br I Br I

Cl I Cl I

                 

2 2 6 2 2 3 10

nau Iot bien mat

(18)

X

(19)

(20)

F

F22 Fluorine (Latin fluo, “flow”), symbol F, chemically reactive, poisonous gaseous element The atomic number of fluorine is

Fluorine occurs naturally in the combined form as

fluorite-CaF

fluorite-CaF22, cryolite-, cryolite-Na

Na33AlFAlF66, and apatite-, and apatite-Ca

Ca55(PO(PO44))33FF Fluorite, from which most fluorine compounds are generally derived, is commonly mined in the United States from large deposits in northern 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 animals It is the 17th element in order of abundance in the crust of the earth

1886

French chemist

Henri Moissan.

(21)

CaF

(22)

Na

Na33AlFAlF66

Cryolite

Cryolite, mineral, sodium aluminum fluoride (Na3AlF6) Cryolite has a hardness of 2.5 and a specific gravity of about 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

(23)

Ca

Ca55(PO(PO44)F)F

Apatite

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

(24)

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 electrolytic

techniques (KHF

techniques (KHF22, HF – , HF –

100

100 00CC

, and liquid fluorine may be prepared by passing the gas through a metal or rubber tube surrounded by liquid air

F

(25)

Fluorine compounds have many applications The chlorofluorocarbons, odorless and nonpoisonous liquids or gases such as Freon-CFClFreon-CFCl33, 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, TeflonTeflon, 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 petroleum are useful as highly stable lubricating oilslubricating oils Uranium

hexafluoride, the only volatile compound of uranium, is used in the gaseous gaseous

diffusion

diffusion process to provide fuel for atomic power plants

(26)

Cl

Cl22Chlorine, 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 1810 that the

British chemist Sir

Humphry Davy

Humphry Davy proved that chlorine was an

element and gave it its present name.

(27)

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).

KCl, Potassium Chloride

HALITE NaCl, Sodium Chloride

2 2 2

2NaCl  2H O    comangngandienphan 2NaOH Cl  H 

2 2 2 2

(28)

Most chlorine is produced by the

electrolysis of ordinary salt solution, with sodium hydroxide as a by-product

(29)

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

Br

Br22

2 2 2 2

Cl Br  Cl  Br

(30)

I

I22 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, Without iodine, stunted growth and conditions

stunted growth and conditions

such as goiter can result

such as goiter can result Thus in 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 other uses

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

3 3 4 4 2 2

2IO 5HSO 3HSO 2SO  H O I

(31)

At

At22 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

high-energy 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

(32)

3.Điều chế ứng dụng

4.Hidro halogenua

(33)

HX

. . .

HX aq H  aq X  aq

 

( ) ( ) ( ) ( ) ( )

HX k aq H k X k aq H k X k aq

        

0 0 0 0 0 0 0

HX H X H X

h LK I A h h

G G G G G G G

(34)

HF

HF HClHCl HBrHBr HIHI

EH-X

[kJ/mol]

565 431 364 297

23.9 535.1 1320.2 -347.5 -1513.6 18.1 -4.2 404.5 1320.2 -366.8 -1393.4 -39.7 -4.2 339.1 1320.2 -345.4 -1363.7 -54.0 -4.2 272.2 1320.2 -315.3 -1330.2 -57.3 HX h G   LK G  H I G  X A G  H h G   X h G   G  7.2 10 5.1 K K H bonding

HF H O F H O

F HF HF

                                   

HF axít yếu

HCl, HBr, HI axit mạnh

(35)

 

2 4 2

4 2 6

2 2 6 2

4 2

2

6 2

HF SiO SiF H O

HF SiF H SiF

HF SiO H SiF H O

   

  

   

4 2

2 2

3 2

16 5 2 2 8

2 2

8 4 4

2 2 2 2

HCl KMnO Cl MnCl KCl H O HBr H SO SO Br H O

HI H SO H S I H O HI FeCl FeCl I HO

(36)

Hydrogen Chloride

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: vol of water at 20° C absorbs 442 vol of hydrogen chloride gas at atmospheric pressure The resulting solution—hydrochloric acid—contains 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

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

(37)

2

2 2 2

burn

RH Cl RCl HCl H Cl HCl

   

  

,

3 3 3 3 3

X Br I

PX HOH  H PO HX

     

2 2 4( ) 4 2

CaF  H SO dac   CaSO  HF

HF

HCl

HX

(38)

(39)

Covalent Oxides F2O, Cl2O and Cl2O7

F2O(g) + H2O(l)  2HF(aq) + O2(g) Cl2O(g) + H2O(l)  2HOCl(aq)

Cl2O7(l) + H2O(l)  2HClO4(aq)

Cl

O O

Cl O

O O Cl2O7(g)/(l)

Cl

O O

Cl O

O O

+

-Cl2O7(s)

(40)

NAMING OXOANIONS - EXAMPLES

Prefixes Root Suffixes Chlorine Bromine Iodine

per “ ” ate perchlorate perbromate periodate [ ClO4-] [ BrO

4-] [ IO4-] “ ” ate chlorate bromate iodate [ ClO3-] [BrO

3-] [ IO3-] “ ” ite chlorite bromite iodite [ ClO2-] [ BrO

2-] [ IO2-] hypo “ ” ite hypochlorite hypobromite hypoiodite [ ClO -] [ BrO -] [ IO -]

N

o.

o

f

O

a

to

m

(41)

HOCl

Axit Hipocloro

Kém bền

Nước Javen

2

Cl  HOH    HCl HOCl

anh sang mat troi

2 xuc tac, chat khu

2HOCl      2HCl O

2

CaCl

2 2

chat hut nuoc

2HOCl     H O Cl O

dun nong, de xay ra

3

3HOCl       2HCl HClO

KClO

KClO33

Kali clorat

Thuốc nổ

CaOCl

(42)

HOCl

Hipoclorit

Nước Javen

Nước Javen NaCl NaOCl  2H O2

2 2 ( )

Cl  NaOH nguoi

2

Cl  HOH    HCl HOCl

2NaOH



Điện phân không

màng ngăn dung

dịch nguội NaCl

(43)

CaOCl

CaOCl22

Cl

2 ( )2 2

Cl  Ca OH   Ca H O OCl

HOCl có tính chất oxi hóa mạnh nên nước Javen

và CaOCl

(44)

KClO

KClO33

dun nong, de xay ra

3

3HOCl       2HCl HClO

2

3Cl 6OH nong ( )

 80 80 5Cl  ClO3  3H O2

0

0CC

Axit cloric tồn

trong dung dịch

không 50 %,

axit mạnh, chất oxi

hóa mạnh

Điện phân không

màng ngăn dung

dịch KCl nóng

(45)

3 5 6 3 2 3 2

ClO Cl  H  Cl H O

     

chất oxi hóa mạnh

3 6 6 3 2 3 2

ClO I  H  Cl  I H O

     

Ion clorat oxi hóa Cl

Ion clorat oxi hóa Cl , Br, Br , I, I môi trường axit môi trường axit

Không xảy mơi trường trung tính, kiềm

(46)

2

3 250 2

2 ( ) o 2 3

MnO C

KClO r    KCl  O 

3 4

4KClO r( )    nhietkocao 4KClO  KCl

Axit pecloric axit mạnh axit

P, S, C

Ngòi nổ

Pháo hoa

Diêm (50 % KClO

(47)

• 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

(48)

• 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 Name as Name as

Symbol Stem First Element (A) Second Element (B) O ox- oxygen oxide

(49)

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

Greek Prefixes

mono- = (often omitted) hexa- = 6 di- = hepta- = 7 tri- = octa- = 8 tetra- = nona- = 9 penta- = deca- = 10 Examples:

PF5 = phosphorus pentafluoride HCl = hydrogen chloride

N2O5 = dinitrogen tetraoxide

Note: many

compounds have

Định dạng
Số trang	49
Dung lượng	3,99 MB