Chapter 3.

Stoichiometry

3.1. Introduction 3. 2. Atomic Masses 3.3. The Mole 3.4. The Molar Mass 3.5. Percent Composition of Compounds 3. . !eterminin" the #ormula of a compound 3.$. Chemical %&uations 3.'. (alancin" Chemical %&uations 3.). Stoichiometric Calculations 3.1*. Calculations in+ol+in" a limitin" ,eactant and a percent yield

3. 1. Introduction Chemical reactions have a profound effect on our live. - Foods transformed to energy. - cancer is induced in humans by substances in our environment. Reactions involved the quantities of materials consumed and produced. This area of study is called chemical stoichiometry. To understand chemical stoichiometry you must first understand the concept of relative masses. 3.2. Atomic Masses The first quantitative information about atomic masses came from the work of alton! "ay-#ussac! #avoisier! $vogadro and %er&elius. ' mass of 1()1amu* The modern system of atomic masses is based on carbon twelve 1+C as a standard in this system. 1+C is assigned a mass of e,actly 1+ atomic mass units 'amu*. The masses of other atoms are given relative to this standard. -Carbon 'C* ././.0 1+C1 1.110
12

C1 34.410 15C6

Carbon atomic mass ) 1+.41 amu 'also called average atomic mass* 7nit ) atomic mass unit. amu or dalton. $bsolute si&es of atoms8 9ass of ( atom) 1.::4;5 , 14-+5g. <olume of ( atom ) +.1 , 14-+;cm2. 1 amu ) 1.::4;5 , 14=+5 g

>article

Charge

9ass 'g*

9ass 'amu*
+

>roton Aeutron Blectron

?1 Aeutral -1

1.:@+@,14-+5 1.:@;4,14-+5 ..14.,14-+/

1.44@2 1.44/@ ;.5/: , 14-5

#BA"T( = $A"CTRD9 'E* ) 14-14m Typical atomic dimensions are 1 to ; ,14-14 m which corresponds to 1 to ; E.

3.2.1. A+era"e Atomic Mass

Pro-lem
2

Aaturally occurring chlorine has two isotopes! 2;1@Cl! 2@1@Cl. The 2;-Cl isotope has a relative atomic mass of 25..://amu and an abundance of @;.@@0 and the 2@-Cl isotope has a relative atomic mass of 2:..:;.amu and an abundance of +5.+20. Calculate the average atomic mass of Cl. Solution $verage $tomic 9ass of Cl ) '4.@;@@,25..:;.* ? '.+5+2,2:..:;.* ) 2;.5;+@ umaFatom 3.2.2. Molecular Mass The molecular mass is the summery of the atomic masses of the atoms that make up the molecule. B,ample. The chemical formula for water is CD+ 9ass of C ) 1+.41 amu 9ass of D ) 1;... amu Gts relative molecular mass ) '1+.41* ? +'1;...* ) 52... amu 3.2.3. ,elati+e Atomic Mass $ relative scale has been developed to compare the relative masses of atoms. The $TD9GC 9$CC of an atom is its relative mass on this scale. Carbon- 1+ '1+C* has been set as the standard and assigned a RB#$TG<B 9$CC of e,actly 1+. Relative atomic masses have no units since they are the ratio of two masses. 2.+.5. Relative 9olecular 9ass

 The relative molecular mass is the sum of the relative atomic masses of the atoms that make up the molecule. B,ample! the chemical formula for water is (+D Gts relative molecular mass ) + '1.44@.5* ? 1;....5 ) 1/.41;2 3.3. The Mole $ mole has been defined as a unit containing :.4++12@ , 14 +2 ! $vogadroHs number! atoms or molecules. Dne mole of any atom or molecule contains the same number of atoms or molecules. $vogadroIs Aumber $vogadroIs number8 the number of atoms in e,actly 1+ g of 1+C. Ao ) :.4++12@ , 14+2 1mole 1+C weigts 1+g and contains A4 atoms. Codium 'Aa* has a relative atomic mass of ++../.@@

Gf Ao atoms of 1+C have a mass of 1+g then! the mass of A o atoms of sodium must be '++../.@@*F1+ ,1+g ) ++../.@@ g 1mole of sodium weigts ++../.@@g The mass! in grams! of Ao atoms of $AJ element is numerically equal to the relative atomic mass of that element. Came applies to molecules. Cince the relative molecular mass of water is 1/.41;+! the mass of A o water molecules is 1/.41;+g.

%.ercise 1. Calculating number of atom $ silicon chip used in an integrated circuit of a microcomposer has a mass of ;.:/mg how many silicon 'Ci* atoms are present in the chipK 9olar mass of silicon ) 9Ci) +/.4.g Colution The strategy for doing this problem is to convert from milligrams of silicon to grams of silicon then to moles of silicon and finally to atom of silicon.

%.ercise 2. How many moles and atoms of Fe are there in 8.232 g of Fe? (M Fe= 55.85g.mol-1) Colution

%.ercise 3. (ow many grams of water are there in 4.+444 moles of waterK '9 (+D ) 1/.41;g.mol-1* Colution 4.+444 mol (+D , 1/.41; g.mol-1 (+D ) 2.:42 g (+D

3.4. The Molar Mass The 9olar 9ass is the mass! in grams! of one mole of atoms or molecules is numerically equal to relative atomic or molecular masses. (ence 1 mole of Aa weighs ++.././ g! 1 mole of ( +D weighs 1/.41;2 g or g.mol-1.

Mole ,elationships in Chemical #ormulas Cince we count atoms and molecules in mole units! we can find the number of moles of a constituent element if we know the number of moles of the compound. 9oles of compound 1 mol AaCl 1 mol (+D 1 mol CaCD2 1 mol C:(1+D: 9oles of constituents 1 mol Aa! 1 mol Cl + mol (! 1 mol D 1 mol Ca! 1 mol C! 2 mol D : mol C! 1+ mol (! : mol D

3.5. Percent Composition of Compounds

/

 Mass percent of an element/

m ass % =

m ass of elem ent in com pound 100% m ass of com pound

For iron in iron 'GGG* o,ide! 'Fe+D2*

m a s s%F e =

1 1 16 . 9 1 0 0 %= 6 99 . 4 % 1 5 96 . 9

%mpirical #ormulas The simplest! whole-number ratio of atoms in a molecule is called the 'empirical formula*. Can be determined from percent composition or combining masses. The molecular formula is a multiple of the empirical formula. molecular formula ) 'empirical formula*n -n ) integer6 molecular formula ) C:(: ) 'C(*: empirical formula ) C( B,amples (ydrogen >ero,ide 9olecular formula ) (+D+ Bmpirical formula ) (D

%en&ene
.

9olecular formula ) C:(:

Bmpirical formula ) C( "lucose 9olecular formula ) C:(1+D:

Bmpirical formula ) C(+D

%mpirical #ormula !etermination Cince mass percentage gives the number of grams of a particular element per 144g of compound! base the calculation on 144g of compound! each percent will then represent the mass in grams of that element. etermine the number of mole of each element present in 144g of compound using the atomic masses of the elements present. ivide each value of the number of moles by the smallest of the values

Gf the numbers obtained in the previous step are not whole numbers! multiply each number by an integer so that the results are all whole numbers %.ample/ Find the empirical formula of aspirin with the given mass percent composition. Lrite down the given quantity and its units. "iven8 C ) :4.440 ( ) 5.5/0 D ) 2;.;20

14

Therefore! in 144 g of aspirin there are :4.44 g C! 5.5/ g (! and 2;.;2 g D. Gnformation8 "iven8 :4.44 g C! 5.5/ g (! 2;.;2 g D

Lrite down the quantity to find andFor its units. Find8 empirical formula! C (yD! Collect needed conversion factors8 1 mole C ) 1+.41 g C 1 mole ( ) 1.41 g ( 1 mole D ) 1:.44 g D Lrite a solution map8

$pply the solution map8 Calculate the moles of each element.

60.00 g C 1 mol C = 4.996 mol C 12.01 g C 1 mol H = 4.44 mol H 1.01 g H 1 mol O = 2.221 mol O 16.00 g O

4.48 g H

35.53 g O

$pply the solution map8

11

Lrite a pseudoformula.

$pply the solution map8 Find the mole ratio by dividing by the smallest number of moles.

C 4.996 H 4.44 O 2.221

2.221 2.221 2.221

C 2.25 H 2O1
Molecular #ormulas The molecular formula is a multiple of the empirical formula. To determine the molecular formula! you need to know the empirical formula and the molar mass of the compound.

3. . Chemical %&uations
1+

3. .1. Chemical reaction Chemical reaction is a chemical change involves a reorgani&ation of the atoms in one or more substances. $ representation of a chemical reaction8 C+(;D( 'l* ? 2D+ 'g* +CD+ 'g* ? 2(+D 'l* reactants products

A(2'g* ? D+'g* M AD'g* ? (+D'g* Aotes that the atoms have been reorgani&ed1 %onds have been broken! and new ones have been formed! Gn a chemical reaction! atoms are neither created nor destroyed! all atoms present in reactants are present in the products.

3.$. (alancin" Chemical %&uations C+(;D( ? 2D+ +CD+ ? 2(+D 1 mole of ethanol reacts with 2 moles of o,ygen to produce + moles of carbon dio,ide and 2 moles of water

12

The identities of the reactants and products must not be changed. The formulas of the compounds must not be changed in balancing a chemical equqtion.

%.amples
15

1. NNAaCl ? NN%eF+ --O NNAaF ? NN%eCl+ +. NNFeCl2 ? NN%e2'>D5*+ --O NN%eCl+ ? NNFe>D5 2. NN$gAD2 ? NN#iD( --O NN$gD( ? NN#iAD2 5. NNC(5 ? NND+ --O NNCD+ ? NN(+D ;. NN9g ? NN9n+D2 --O NN9gD ? NN9n Solutions for the e.amples 1. + AaCl ? 1 %eF+ --O + AaF ? 1 %eCl+ +. + FeCl2 ? 1 %e2'>D5*+ --O 2 %eCl+ ? + Fe>D5 2. 1 $gAD2 ? 1 #iD( --O 1 $gD( ? 1 #iAD2 5. 1 C(5? + D+ --O 1 CD+ ? + (+D ;. 2 9g ? 1 9n+D2 --O 2 9gD ? + 9n 3. '. Stoichiometric Calculations 1. %alance the equqtion for the reaction. +. Convert the known mass of the reactant or product to moles of that substance. 2. 7se the balanced equation to set up the appropriate molar ratios. 5. 7se the appropriate molar ratios to calculate the number of mole of the desired reactant or product. ;. Convert from moles back to grams if required by the problem.

Calculatin" Mass of ,eactants and Products

1;

1:

3.). Calculations In+ol+in" a 0imitin" ,eactant The limiting reactant is the reactant that is consumed first! limiting the amounts of products formed.

1@

1/

The amount of a product formed when the limiting reactant is completely consumed is called the theoretical yield of that product The actual yield of product is often given as a percentage of the theoretical yield. This is called the percent yield >ercent yield ) $ctual yield , 1440

Theoretical yield

1.

Chapter 4

Types of Chemical ,eactions and Solution Chemistry

4.1. 1ater2 the common sol+ent. 4.2. The 3ature of A&ueous Solutions/ Stron" and 1ea4 electrolytes. 4.3. The Composition of Solutions. 4.4. Types of Chemical ,eactions. 4.5. Precipitation ,eactions. 4. . !escri-in" ,eactions in Solutions 4.$. Stoichiometry of Precipitation ,eactions 4.'. Acid5(ase Titrations. 4.). 6.idation5,eduction ,eactions. 4.1*. (alancin" 6.idation5,eduction ,eactions.

4.1. 1ater2 the common sol+ent

+4

 Later is one of the most important substances on earth Dne of the most valuable properties of water is its ability to dissolve many different substances.

Later is a dissolving medium! or a solvent. issolved substance is a solute such as salt 'AaCl! 9gF +! PAD2! Q* in weak amount

Lhen ionic substances dissolve in water they break up into individual cations and aninons Later is RbentS or <-shaped. The D-( bonds are covalent. Later is a polar molecule. (ydration occurs when salts dissolve in water. Colubility depends on salts nature The differences in solubilities of ionic compounds in water typically depends on the relative attractions of the ions for each other.

+1

>olar water molecules interact with positive and negative ions of a salt assisting in the dissolving process.

Bthanol is very soluble in water because of the presence of similar polar D-( bond in the tow compounds. 4.2. The 3ature of A&ueous Solutions/ Stron" and 1ea4 electrolytes. Dne useful property for characteri&ing a solution is its electrical conductivity. Came aqueous solutions conduct current +ery efficiently1 they contain stron" electrolytes. Dther solutions conduct only a small current7 they contain 8ea4 electrolytes. Came solution permit no current flo8 they are non electrolytes.

++

1hen 3aCl dissol+es in 8ater2 the Cl5 ions and Sodium ions 3a9 spread randomly. The solution conducts electricity/ The solution contains electrolytes

'a*Ctrong electrolytes8 Cubstances completely ioni&ed in water 'b*Leak electrolytes 8 Cubstances partially ioni&ed in water or contain few ions 'c* Aon electrolytes 8substances contain no ions

+2

Stron" electrolytes Salts / Totally ioni&ed in water to give cations and anoins Stron" acids 8 Totally ioni&ed in water to give (? :Cl :363 :2S64
(+D (+D (+D

:9;a&< 9 Cl5 ;a&< :9 ;a&< 9 3635;a&<

:9 ;a&< 9 :S645 ;a&<

Stron" -ases/ Totally ioni&ed in water to give D(ions. (+D

AaD( 's* PD( 's* (+D Aa?'aq* ? D(- 'aq* P?'aq* ? D(- 'aq*

1ea4 electrolytes Leak electrolytes are substances that e,hibit a small degree of ioni&ation in water Leak acids - dissociate to a slight e,tent to give (? in solution (C+(2D+ 'aq*
(+D

(? 'aq* ?

C+(2D+- 'aq*

1ea4 -ases8 react only slightly with water to give ions D(-. A(2 'aq* ? (+D 'l* 3onelectrolytes Aonelectrolytes are substances that dissolve in water but do not produce any ions! A(5?'aq* ? D(- 'aq*

+5

4.3. The composition of Solutions Chemical reaction often take place when two solutions are mi,ed. $ solution is generally composed by8 A Solute dissolves in water 'or other RsolventS* changes phase 'if different from the solvent* is present in lesser amount 'if the same phase as the solvent* Sol+ent retains its phase 'if different from the solute* is present in greater amount 'if the same phase as the solute* The concentration of a solution can be described in many different ways. Le limit on the morality Molarity 9olarity 'M* 8 moles of solute per volume of solution in liters 7nits8 mol.#-1 Common Terms of Solution Concentration Ctandard Colution8 a solution of e,act known concentration! prepared by dissolving a definite weight of solute in a volumetric flask Ctock 8 routinely used solutions prepared in concentrated form. Concentrated 8 relati"ely large ratio of solute to solvent. ';.4 M AaCl* ilute8 relati"ely small ratio of solute to solvent. '4.41 M AaCl*

+;

+:

Cteps involved in the preparation of a standard aqueous solution a* >ut a weighted amount of substances 'solute* b* issolve the solid in water by gently swirling the flask

c* $dd more water until the level of the solution Tust reaches the mark etched on the neck of the flask. !ilution / $ddition of water 'solvent* to a concentrated solution to get a less concentrated one #aw of ilution 8 where8

91 , <1 ) 9+ , <+

91 U <1 ) 9olarity and volume before dilution 9+ U <+ ) 9olarity and volume after dilution

+@

4.4. Types of Chemical ,eactions >recipitation reactions $gAD2'a#* ? AaCl'a#* A"Cl's* ? AaAD2'a#* $cid-base reactions AaD('a#* ? (Cl'a#* AaCl'a#* ? (+D'l* D,idation-reduction reactions Fe+D2's* ? $l's* Fe'l* ? $l+D2's* 4.5. Precipitation ,eactions Lhen two solutions are mi,ed! an insolu-le substance sometimes forms. Cuch a reaction is called a precipitation reaction! and the solid that forms is called a precipitate.

%.ample 1/

+/

Lhen >otassium Chromate P+CrD5 is added to a solution of %arium Aitrate %a'AD2*+! a yellow precipitate of %arium Chromate %aCrD5 is formed. P+CrD5'aq* ? %a'AD2*+'aq* PAD2'aq* ? (aCr64;s< P? 'aq* ? AD2-'aq* ?

+P? 'aq* ? CrD5+-'aq* ? %a?+'aq* ? +AD2-'aq* (aCr64;s<

? ?

Lhen >otassium chromate P+CrD5 is added to a solution of %arium nitrate %a'AD2*+! a yellow precipitate of %arium chromate %aCrD5 is formed. %.ample /2 $gAD2'aq* ? PCl'aq* $g? 'aq* ? AD2-'aq* ? P?'aq* ? Cl-'aq* PAD2'aq* ? $gCl's* P? 'aq* ? AD2-'aq* ? $gCl's*

Lhen Cilver nitrate solution $gAD2 is added to a solution of >otassium chloride PCl! a white precipitate of Cilver chloride is formed $gCl. Simple ,ules for Solu-ility
+.

1. 9ost nitrate 'AD-2* salts are soluble. +. 9ost alkali 'group 1$* salts and A(5? are soluble. 2. 9ost Cl-! %r-! and G- salts are soluble. 'ADT $g?! >b+?! (g++?* 5. 9ost sulfate salts are soluble. 'ADT %aCD5! >bCD5! (gCD5! CaCD5* ;. 9ost D(- salts are only slightly soluble 'AaD(! PD( are soluble! %a'D(*+! Ca'D(*+ are marginally soluble. :. 9ost C+-! CD2+-! CrD5+-! >D52- salts are only slightly soluble. 4. . !escri-in" ,eactions in Solutions 1. 9olecular equation gives the overall reaction stoichiometry but not necessarily the actual forms of the reactants and products in solution. $gAD2'a#* ? AaCl'a#* $gCl's* ? AaAD2'a#* +. Complete ionic equation 'all reactants and products are strong electrolytes* $g?'a#* ? AD2-'a#* ? Aa?'a#* ? Cl-'a#* $gCl's* ? Aa?'a#* ? AD2-'a#* 2. Aet ionic equation 'show only ions that actually react* $g?'a#* ? Cl-'a#* $gCl's* Aa? and AD2- are spectator ions. 4.$. Stoichiometry of Precipitation ,eactions !eterminin" of the mass of product formed Calculate the mass of solid AaCl that must be added to 1.;4# of a 4.1449 $gAD2 solution to precipitate all the $g ? ions in the form of $gCl.
24

Solution Lhen added to $gAD2 solution 'which contains $g? and AD2- ions*! the solid AaCl dissolves to yield Aa? and Cl- ions. Thus the mi,ed solution contains the ions $g? AD2Aa? Cl-

Aotes that AaAD2 is soluble and $gCl is insoluble. Therefore $gCl forms according to the following net ionic equation. $g? ? Cl$gCl's*

Gn this case we must add enough Cl- ions to react with $g? ions present. Thus we must calculate the moles of $g ? present in 1.; # of 4.1449 $gAD2 solution. 1.;4# , 4.144 mol $g? F# ) 4.41; mol $g?

%ecause $g? and Cl- react in a 181 ratio! 4.1;4 mol Cl - ions AaCl are required. Le calculate the mass of AaCl requied as follows. 4.'. Acid5(ase Titrations %rVnsted '1/@.-1.5@* Acid/ a chemical entity that gives proton (? (ase/ a chemical entity that accept proton (? (Cl'aq* ? AaD('aq*

(+D'aq* ? AaCl'aq*

'(? 'aq*? Cl-'aq*?* ? 'Aa?'aq*? D(-'aq* * (? 'aq* ? D(-'aq*

(+D'aq* ? Cl-'aq*? Aa?'aq*

(+D'l*

Performin" Calculations for Acid5(ase ,eactions 1. #ist initial species in the combined solution before any reaction occur. +. Lrite balanced net ionic equation for this reaction.
21

2. Calculate moles of reactants. 7se the volume of the original solutions and their molarities. 5. etermine the limiting reactant. ;. Calculate moles of required reactant or product. :. Convert to grams or volume! as required.

Lhen a Tust enough base is added to react e,actly with the acid in a solution we say the acid has been neutrali&ed.

Acid5(ase Titrations <olumetric analysis is a technique for determining the amount of certain substance by doing a titration. $ titration involves delivery 'from a buret* of a measured volume of a solution of known concentration 'the titrant* into a solution containing the substance being analy&ed 'the analyte*. Lhen the analyte is totally consumed by the titrant the equivalent point is achieved. This point is often marked by an indicator. The end-point or R equivalent-point S is the point at which the number of equivalents of titrant and analyte are equal.

The indicator
2+

The indicator is a weak organic acid or organic base! its color depends on acidic or basic nature of the analyte during the titration process >henolphthaline 8 is colorless in acidic medium and pink in base medium while 9ethyl Drange is orange in a base medium and red in acidic medium.

4.). 6.idation5,eduction ,eactions 23a;s< 9 Cl2 ;"< 23aCl ;s<

Reaction like this in which one or more electrons are transformed are called o.idation5reduction reaction or redo. reactions 4.). 1. 6.idation state ; 6.idation num-er * 6.idation state is a positive or negative number assigned to an atom to indicate its degree of o,idation or reduction.
22

"enerally! a bonded atomIs o,idation number is the charge it would have if the electrons in the bond were assigned to the atom of the more electronegative element. . D,idation state of an atom in an element ) 4 . D,idation state of monatomic element ) charge . D,ygen )-+ in covalent compounds 'e,cept in pero,ides where it )-1* . ( ) ?1 in covalent compounds . Fluorine ) -1 in compounds . Cum of o,idation states ) 4 in compounds. . Cum of o,idation states ) charge of the ion. 4.). 2. ,ules for Assi"nin" 6.idation 3um-ers 1* The o,idation number of any uncombined element is &ero. +* The o,idation number of a monatomic ion equals its charge.
2 Na + Cl 2 2 Na Cl
0 0 +1 1

2* The o,idation number of o,ygen in compounds is -+! e,cept in pero,ides! such as (+D+ where it is -1. 5* The o,idation number of hydrogen in compounds is ?1! e,cept in metal hydrides! like Aa(! where +it 1 is 2 -1. H2O ;* The sum of the o,idation numbers of the atoms in the compound must +2 2 +1 +1 2 equal 4. Ca (O H ) 2 H2O :* The sum of the o,idation numbers in the formula of a polyatomic ion is equal to its ionic charge.

N O3

? 2

25

#osing 4.). 3. The characteristics of 6.ydo5reduction reaction D,ydo-reduction reaction are characteri&ed by a transfer of electrons. Gn some cases it occurs in a lateral sense to form ions 9g's* ? C's* M 9gC's* 9g is the reducing agent1 9g is o,idi&ed 'looses electrons and becames 9g+?*. C is the o,idi&ing agent1 C is reduced ' gains e- and becames C +-* Cometimes the transfer is less o-+ious C(5'g* ? +D+'q* '-5* '?1* C(5 4 CD+ ? /e2;

CD+'g* ? +(+D'g* ?5 -+ ?1 -+

-5

?5

+D+ ? /e4

CD+ ? +(+D 5'-+* ) -/

Carbon is o,idi&ed8 increase in its o,idi&ing state D,ygen is reduced8 decrease in its o,idi&ing state C(5 is the reducing agent and D+ is the o,idi&ing agent

- #oosing electrons is o.idation! and the substance that loses the electrons is called the reducing agent. - "aining electrons is reduction! and the substance that gains the electrons is called the o,idi&ing agent.

Cummary of an o,ydoreduction process! in which 9 is o,idi&ed and W is reduced

2:

4.).

(alancin" 6.idation5,eduction ,eactions

(alancin" -y :alf5,eaction Method

1. Write separate reduction, oxidation reactions. 2. For each hal !reaction" #alance ele$ents %except H, O& #alance O usin' H2O #alance H usin' H( #alance char'e usin' electrons

3. ) necessar*, $ultipl* +* inte'er to e,uali-e electron count. 4. 5. .dd hal !reactions. Chec/ that ele$ents and char'es are +alanced.

Half-Reaction Metho - !alancing in !a"e

1.

#alance as in acid.

2. .dd OH! that e,uals H( ions %+oth sides0& 3. For$ 1ater +* co$+inin' H(, OH!. 4. Chec/ ele$ents and char'es or +alance.

=A,IA(0% =A0%3C% %0%M%3TS

2@

 Culfur8 CD5+-'?:*! CD2+-'?5*! C'4*! FeC+'-1*! (+C'-+* Carbon8 CD+'?5*! C'4*! C(5'-5* Aitrogen8 AD2-'?;*! AD+-'?2*! AD'?+*! A+D'?1*! A+'4*! A(2'-2* Gron8 Fe+D2'?2*! FeD'?+*! Fe'4* 9anganese8 9nD5-'?@*! 9nD+'?5*! 9n+D2'?2*! 9nD'?+*! 9n'4* Copper8 CuD'?+*! Cu+D'?1*! Cu'4* Tin8 CnD+'?5*! Cn+?'?+*! Cn'4* 7ranium8 7D++?'?:*! 7D+'?5*! 7'4* $rsenic8 (2$sD54'?;*! (2$sD24'?2*! $s'4*! $s(2'-1* Chromium8 CrD5+-'?:*! Cr+D2'?2*! Cr'4* "old8 $uCl5-'?2*! $u'CA*+-'?1*! $u'4*

2/

#tomic "t$%ct%$e an it" &e$io icit'

Chapter 5.

Chapter content %lectroma"netic radiation 3ature of matter The atomic spectrum of hydro"en The (ohr>s model The &uantum model of the atom The &uantum num-ers 6r-itales chapes and ener"y %lectron spin and the pauli principle Polyelectronic atom The history of the periodic ta-le The auf-au principle and the periodic ta-le Periodic trends in atomic properties

2.

5.1. %lectroma"netic radiation Radiant energy that e,hibits wavelength-like behavior and travels through space at the speed of light in a vacuum is called electromagnetic radiation. Blectromagnetic radiation is composed by a two perpendicular electro and magnetic field. 1a+es 1. Lavelength 8 distance between two peaks in a wave. +. Frequency8 number of waves per second that pass a given point in space. 2. Cpeed 8 speed of light is +...@. 14/ mFs.

The nature of 8a+es. Aote that the radiation with the shortest wavelength has the highest frequency. Lavelength and frequency can be interconverted.

) $F
54

 ) frequency 's-1*

) wavelength 'm*

$ ) speed of light 'm s-1*

Radiation provides an important means of energy transfer. #i"ure $.2. Classification of electroma"netic radiation.

51

5.2. The nature of matter $t the end of the 1. th century! the idea prevailed that matter and energy were distinct. 9atter was thought to consist of particles with masses and positions in space. Bnergy in the form of light 'electromagnetic radiation* was described as a wave with no masse and no position.
Ma. Planc4 ;1'5'51)4$<

9atter can absorb and emit any quantity of energy. The transfer of energy for a system can be8

E = h =

hc

5+

% ) change in energy! in X

h ) >lanckIs constant! :.:+: , 14-25 X s n ) frequency! in s-1 l ) wavelength! in m Transfer of energy is quanti&ed! and can only occur in discrete units! called a quantum. Al-ert %instein ;1'$)51)55< Blectromagnetic radiation can be viewed as a stream of particles called photons. The energy of each photon is given by B photon ) h ) hcF evelopped also by % ) m$+ E ) energy! m ) mass! c ) speed of light Bnergy has a mass m ) %&$+ m)B Fc+) hcFc+)hFc

Bphoton ) hcF mphoton ) hFc

1a+elen"th and Mass de %roglieIs Bquation

h = m

52

For a particle with a velocity v. where! ) wavelength! in m 1 h ) >lanckIs constant! :.:+: , 14-25 X,s-1 ) kg m+ s-1 1 m ) mass! in kg 1 ) frequency! in s-1 5. 3. Atomic Spectrum of :ydro"en Continuous spectrum8 Contains all the wavelengths of light. #ine 'discrete* spectrum8 Contains only some of the wavelengths of light.

The hydrogen spectrum indicates that only certain energy are allowed for the electron in the hydrogen atom. The energy of the electron in the hydrogen atom is quanti&ed. Changes in energy between discrete energy levels in hydrogen will produce only certain wavelengths of emitted light.

55

5. 4. The (ohr Model

3iels (ohr ;1''551) 2<

The electron in a hydrogen atom moves around the nucleus only in certain allowed circular orbits. The energy levels available to the electron in the hydrogen atom is given by

E = 2.178 10 18 J ( z 2 / n 2 )
'here( % ) energy of the levels in the ( atom (! ! ) 1* n ) integer. ) ) nuclear charge 'for an

5;

For

n) 1! the electron has more negative energy than it does for n ): means that the electron is more ti"htly -ound in the smallest allowed orbit. The change in energy *% when the ele$tron falls from n=+ to n=1 is *% ) %final state - %initial state ) B1 - B:

0imits of the (ohr>s model

The energy levels calculated by %ohr closely agreed with the values obtained from the hydrogen emission spectrum. Lhen %ohrIs model was applied to atoms other than hydrogen it
5:

hc model = %ohrIs appeared to be very promising. E

did not work at all. Blectrons do not move around the nucleus in circular orbits with quantified energy. 5.5. The ?uantum Mechanical model of the atom The new approach for the atoms is given by the quantum mechanics %ased on the wave properties of the electron $t each electron is associated a function wave . ChrVdungerIs equation

= E H

) The wave function is a function of the coordinates ',! y! &* of the electron position in 2 space ) mathematical operator

% ) total energy of the atom $ specific wave function is often called an orbital characteri&ing its properties. There is a fundamental limitation to Tust how precisely we can know both the position and the momentum 'mv* of a particle at a given time. (eisenberg 7ncertainty >rinciple Lhere , ) position ) momentum ( xm" mv )

The more accurately we know a particleIs position! the less accurately we can know its momentum. Pro-a-ility !istri-ution

h h ) >lanckIs constant 4

5@

Cquare of the wave function probability of finding an electron at a given position Radial probability distribution is the probability distribution in each spherical shell.

Cross Cection of the (ydrogen 1s Drbital >robability istribution ivided into Cuccessive Thin Cpherical Chells 'b* The Radial >robability istribution 5. . ?uantum 3um-ers ;?3< Lhen we solve the CchrVdinger equation for the hydrogen atom. Le find many waves functions 'orbitals* that satisfy it. Bach of these orbitals is characteri&ed by a series of numbers called quantum numbers which describe the various properties of the orbital. The principal &uantum num-er n has integral value 'n ) 1! +! 2! . . .* related to si&e and energy of the orbital. An"ular Momentum &uantum num-er l has integral values from 4 to n -1 for each value of n. This number is related to shape of the atomic orbital.

5/

=alue of l 0etter used

Ma"netic &uantum num-er ml has integral values between =l and l 'ml ) l to -l* relates to orientation of the orbital in space relative to others orbitals.

5.$. 6r-ital shapes and ener"ies The orbital means a probability distribution

5.

T8o ,epresentations of the :ydro"en 1s2 2s2 and 3s 6r-itals a5The Blectron >robability istribution -5 The Curface Contains .40 of the Total Blectron >robability 'the Ci&e of the Dribital! by efinition*

Representation of the +p orbitals 'a* The Blectron >robability istribution for a +p oribtals. 'b*The %oundary Curface Representations of all Three +p orbitals.

;4

Representation of the 2d Drbitals 'a* Blectron ensity >lots of Celected 2d Drbitals

'b* The %oundary Curfaces of $ll of the 2d Drbitals

Representation of the 5f Drbitals in Terms of Their %oundary Curfaces

5.'. %lectron spin and the Pauli Principle

;1

 Gn a given atom! electrons must be differentiated one from other . two electrons can have the same set of quantum numbers ' n! l! ml*. Therefore! an orbital can hold only two electrons! and they must have different quantum numbers. The solution is given by the electron spin quantum number %lectron Spin &uantum num-er ms 'ms ) ?1F+!-1F+* relates to the spin states of the electrons.

A Picture of the Spinnin" %lectron The Pauli Principle two electrons can not have the same set of quantum numbers ' n! l! ml ( ms *. :und>s ,ule The lowest energy configuration for an atom is the one having the ma,imum number of unpaired electrons allowed by the >auli principle in a particular set of degenerate orbitals.

5.). Polyelectronic atoms

;+

The quantum mechanical model is suitable for the hydrogen atom but not very useful for the other atoms. The quantum mechanical model not consider the attraction and the repulsion between electrons in polyelectronic atoms. Dne especially important difference between polyelectronic atoms and the hydrogen atom is that a given principal quantum level have the same energy 'degenerate*. For polyelectronic atoms! we find for a given principal quantum level the orbitals vary in energy as follows Bns3 Bn,3Bnd3Bnf Lhen electron are placed in a particular quantum level! they prefer the orbitals in the order s! p! d and then f 'lower energies*.

Drbital Bnergy #evels for the (ydrogen $tom 5. 1*. the history of the periodic ta-le The periodic table was originally constructed to present the patterns observed in the chemical properties of the elements $s chemistry progressed during 1/th and 1.th centuries! it became evident that the earth is composed of a great many elements with very different properties.
;2

 First chemists to recogni&e patterns was Xohann obereiner '1@/41/5.*8 Found several groups of three elements that have similar properties. The present form of the periodic table was conceived independently by two chemists1 #othar 9eyer '1/24-1/.;* and imitri Gvanovich 9endeliev '1/25-1.4@*. 5.11. The Auf-au principles and the periodic ta-le The $ufbau principles8 $s protons are added one by one to the nucleus to build up the elements! electrons are similarly added to these hydrogen-like orbitals.

;5

The Blectron Configurations in the Type of Drbital Dccupied #ast for the First 1/ Blements %.amples/ electronic confi"uration
)

#/ 1s22s22p5 P / 1s22s22p 3s23p3

15

Blectron Configurations for >otassium Through Prypton

The Drbitals %eing Filled for Blements in <arious >arts of the >eriodic Table

;;

The >eriodic Table with $tomic Cymbols! $tomic Aumbers! and >artial

Blectron Configurations.

The >osition of the Blements

;:

(road Periodic Ta-le Classifications Representative Blements 'main group*8 filling s and , orbitals 'Aa! $l! Ae! D* Transition Blements8 filling d orbitals 'Fe! Co! Ai* #anthanide and $ctinide Ceries 'inner transition elements*8 filling 5 f and ;f orbitals 'Bu! $m! Bs* 5.12. Periodic trends in atomic properties The model of the atoms is used for several important atomic properties8 ionisation energy! electron affinity! and atomic si&e The ionisation ener"y The quantity of energy required to remove an electron from the gaseous atom or ion. W'g* W?'g* ? e-

Lhere the atom or ion is in its ground state B,ample.

;@

 $l'g* $l?'g* $l+?'g* $l2?'g*

$l?'g* ? e-

G1 ) ;/4PX.mol-1

$l+?'g* ? e- G+ ) 1/1; PT.mol-1 $l2?'g* ? e- G2 ) +@54 PX.mol-1 $l5?'g* ? e- G5 ) 11:44 kT.mol-1

#irst ioni@ation ener"y I1/ increases from left to right across a period1 decreases going down a group %lectron affinity %a The energy change associated with the addition of an electron to a gaseous atom. W'g* ? eAtomic ,adii decrease going from left to right across a period1 increase going down a group. Information Contained in the Periodic Ta-le Bach group member has the same valence electron configuration 'these electrons primarily determine an atomIs chemistry*. The electron configuration of any representative element. W-'g*

Certain groups have special names 'alkali metals! halogens! etc*. 9etals and nonmetals are characteri&ed by their chemical and physical properties.

;/