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Organic Chemistry, 7th Edition L. G. Wade, Jr.

Chapter 4
Estudio de as reacciones !u"#icas

Copyright 2010 Pearson Education, Inc.

Introducci$n
% &odas as reacciones' reactants products % (ecanis#o' ca#ino paso por paso. % )#*itos de un reacci$n'
&er#odin+#ica Cin,tica

Chapter 4

C oraci$n de (etano

% .e!uiere ca or o u/ para su iniciaci$n. % La ongitud de onda #+s e0ecti1a es e a/u , cuando es a*sor*ida por e gas c oro. % (uchas #o ,cu as son producidas por a a*sorci$n de un 0ot$n 2reacci$n en cadena3.
Chapter 4 -

.eacci$n radicaria en cadena


% La iniciaci$n genera un inter#ediario radica ario. % Propagacin' e inter#ediario reacciona con una #o ,cu a esta* e para producir otro inter#ediario reacti1o 2y una #o ,cu a de producto3. % Terminacin' reacci$n !ue destruye e inter#ediario reacti1o.
Chapter 4 4

Iniciaci$n' 5or#aci$n de un +to#o de c oro o0 Ch orine 6to#

7na #o ,cu a de c oro se di1ide ho#o "tica#ente en +to#os de c oro 2radica es i*res3.

Chapter 4

Propagaci$n' Car*$n .adica

E +to#o de c oro choca con una #o ,cu a de #etano y a*strae 2e i#ina3 9, 0or#ando otro radica i*re y uno de os productos 29C 3
Chapter 4 8

Propagaci$n' 5or#aci$n de producto

E radica i*re de #eti o choca con otra #o ,cu a de c oro, produciendo e producto org+nico 2c oruro de #eti o3 y regenerando e radica de c oro.
Chapter 4 7

.eacci$n g o*a

Chapter 4

&er#inaci$n

% 7na reacci$n es c asi0icada co#o ter#inaci$n cuando dos radica es se unen para 0or#ar un en ace co1a ente. % Co#*inaci$n de radica es i*res con conta#inantes u otro tipo de co isiones ta#*i,n son paso de ter#inaci$n.
Chapter 4 ;

&er#inaci$n

Chapter 4

10

Estructuras de Le<is de radica es i*res

% Los radica es i*res son e ectrones sin e#pare=ar.

Chapter 4

11

Constante de E!ui i*rio


% Ke! > ?products@ ?reactants@ % 5or C94 A C 2 C9-C A 9C Ke! > ?C9-C @?9C @ > 1.1 B 101; ?C94@?C 2@ % Large 1a ue indicates reaction Cgoes to co#p etion.D
Chapter 4 12

Ca#*io de energ"a i*re


G > 2energy o0 products3 E 2energy o0 reactants3 G is the a#ount o0 energy a1ai a* e to do <orF. Gegati1e 1a ues indicate spontaneity. Go > ERT2 nKe!3 > E2.-0- RT2 og10Ke!3 <here R > :.-14 JHIE#o and T > te#perature in Fe 1ins.
Chapter 4 1-

5actores !ue deter#inan G


5ree energy change depends on'
Entha py
H> 2entha py o0 products3 E 2entha py o0 reactants3

Entropy
S > 2entropy o0 products3 E 2entropy o0 reactants3

G > H E TS

Chapter 4

14

Enta p"a
% Ho > heat re eased or a*sor*ed during a che#ica reaction at standard conditions. % EBother#ic 2EH3 heat is re eased. % Endother#ic 2AH3 heat is a*sor*ed. % .eactions 0a1or products <ith o<est entha py 2strongest *onds3.
Chapter 4 14

Entrop"a
% So > change in rando#ness, disorder, or 0reedo# o0 #o1e#ent. % Increasing heat, 1o u#e, or nu#*er o0 partic es increases entropy. % Jpontaneous reactions #aBi#i/e disorder and #ini#i/e entha py. % In the e!uation Go > Ho E TSo the entropy 1a ue is o0ten s#a .
Chapter 4 18

Jo 1ed Pro* e# 1
Calculate the value of G for the chlorination of methane.

Jo ution
G = 2.303RT(log Keq) Keq for the chlorination is 1.1 B 1019, and log Keq = 19.04 At 25 C (about 298 Kelvin), the value of RT is RT = (8.314 J/kelvin-mol)(298 kelvins) = 2478 J/mol, or 2.48 kJ/mol Substituting, we have G = (2.303)(2.478 kJ/mol)(19.04) = 108.7 kJ/mol (25.9 kcal>mol) This is a large negative value for G, showing that this chlorination has a large driving force that pushes it toward completion.
Chapter 4 17

KondELissociation Entha pies 2KLE3


% % % % KondEdissociation re!uires energy 2AKLE3. Kond 0or#ation re eases energy 2EKLE3. KLE can *e used to esti#ate H 0or a reaction. KLE 0or ho#o ytic c ea1age o0 *onds in a gaseous #o ecu e.
Homolytic cleavage' When the *ond *reaFs, each ato# gets one e ectron. Heterolytic cleavage' When the *ond *reaFs, the #ost e ectronegati1e ato# gets *oth e ectrons.
Chapter 4 1:

9o#o ytic and 9etero ytic C ea1ages

Chapter 4

1;

Entha py Changes in Ch orination


C9-E9 A C EC
Bonds Broken C EC C9-E9 &M&6LJ

C9-EC

A 9EC
H (per Mole
E4-1 FJ E-41 FJ E7:2 FJ

H (per Mole
A242 FJ A4-4 FJ A877 FJ

Bonds !ormed 9EC C9-EC &M&6L

9N > A877 FJ A 2E7:2 FJ3 > E104 FJH#o


Chapter 4 20

Iinetics
% Iinetics is the study o0 reaction rates. % .ate o0 the reaction is a #easure o0 ho< the concentration o0 the products increase <hi e the concentration o0 the products decrease. % 6 rate e!uation is a so ca ed the rate a< and it gi1es the re ationship *et<een the concentration o0 the reactants and the reaction rate o*ser1ed. % .ate a< is eBperi#enta y deter#ined.
Chapter 4 21

.ate La<
% 5or the reaction 6 A K C A L, rate > kr?6@a?K@*
a is the order <ith respect to 6 * is the order <ith respect to K a A * is the o1era order

% Mrder is the nu#*er o0 #o ecu es o0 that reactant <hich is present in the rateE deter#ining step o0 the #echanis#.
Chapter 4 22

6cti1ation Energy
% &he 1a ue o0 k depends on te#perature as gi1en *y 6rrhenius'

k r = Ae

Ea / RT

<here " > constant 20re!uency 0actor3 #a > acti1ation energy R > gas constant, :.-14 JHFe 1inE#o e T > a*so ute te#perature

#a is the #ini#u# Finetic energy needed to react.


Chapter 4 2-

6cti1ation Energy 2Continued3

% 6t higher te#peratures, #ore #o ecu es ha1e the re!uired energy to react.


Chapter 4 24

Energy Liagra# o0 an EBother#ic .eaction

% &he 1ertica aBis in this graph represents the potentia energy. % &he transition state is the highest point on the graph, and the acti1ation energy is the energy di00erence *et<een the reactants and the transition state.
Chapter 4 24

.ateELi#iting Jtep
% .eaction inter#ediates are sta* e as ong as they donOt co ide <ith another #o ecu e or ato#, *ut they are 1ery reacti1e. % &ransition states are at energy #aBi#u#s. % Inter#ediates are at energy #ini#u#s. % &he reaction step <ith highest #a <i *e the s o<est, there0ore rateEdeter#ining 0or the entire reaction.
Chapter 4 28

Energy Liagra# 0or the Ch orination o0 (ethane

Chapter 4

27

.ate, #a, and &e#perature


X + CH4 HX + CH3

X F Cl Br I

Ea2per (o e3 .ate at 27 NC .ate at 227 NC 4 17 74 140 140,000 1-00 ; B 10E: 2 B 10E1;


Chapter 4

-00,000 1:,000 0.014 2 B 10E;


2:

Jo 1ed Pro* e# 2
Consider the following reaction: This reaction has an activation energy (Ea) of +17 kJ/mol (+4 kcal/mol) and a H of +4 kJ/mol (+1 kcal/mol). Draw a reaction-energy diagram for this reaction.

Jo ution
We draw a diagram that shows the products to be 4 kJ higher in energy than the reactants. The barrier is made to be 17 kJ higher in energy than the reactants.

Chapter 4

2;

Conc usiones
% Cuando au#enta #a, a 1e ocidad dis#inuye. % Cuando au#enta a te#peratura, a 1e ocidad au#enta. % 5 Por reacciona eBp osi1a#ente. % C oro reacciona #oderada#ente. % Kro#o necesitas agregar te#peratura para reaccionar. % Qodo no reacciona 2detecta* e3. Chapter 4

-0

9idr$genos Pri#ario, Jecundario, y &ertiarciario

Chapter 4

-1

(ecanis#o de C oraci$n

Chapter 4

-2

Energ"as de disociaci$n de en aces y de 0or#aci$n de radica es

Chapter 4

--

Jo 1ed Pro* e# Tertiary hydrogen atoms react with Cl about 5.5 times as fast as primary ones. Predict the product ratios for chlorination of isobutane.

Jo ution
There are nine primary hydrogens and one tertiary hydrogen in isobutane.

(9 primary hydrogens) B (reactivity 1.0) = 9.0 relative amount of reaction (1 tertiary hydrogen) B (reactivity 5.5) = 5.5 relative amount of reaction
Chapter 4 -4

Jo 1ed Pro* e# - 2Continued3


Jo ution
Even though the primary hydrogens are less reactive, there are so many of them that the primary product is the major product. The product ratio will be 9.0:5.5, or about 1.6:1.

Chapter 4

-4

Esta*i idad de .adica es

Chapter 4

-8

Ch orination Energy Liagra#

% Lo<er #a, 0aster rate, so #ore sta* e inter#ediate is 0or#ed 0aster.


Chapter 4 -7

.ate o0 Ju*stitution in the Kro#ination o0 Propane

Chapter 4

-:

Liagra#a de energ"a para a *ro#aci$n de propano

Chapter 4

-;

Postu ado de 9a##ond


% .e ated species that are si#i ar in energy are a so si#i ar in structure. % &he structure o0 the transition state rese#* es the structure o0 the c osest sta* e species. % Endothermic reaction' &ransition state is productE iFe. % Exothermic reaction' &ransition state is reactantE iFe.
Chapter 4 40

Energy Liagra#s' Ch orination Rersus Kro#ination

Chapter 4

41

Liagra#as Endot,r#ico y EBot,r#ico

Chapter 4

42

.adica Inhi*itors
% M0ten added to 0ood to retard spoi age *y radica chain reactions. % Without an inhi*itor, each initiation step <i cause a chain reaction so that #any #o ecu es <i react. % 6n inhi*itor co#*ines <ith the 0ree radica to 0or# a sta* e #o ecu e. % Rita#in E and 1ita#in C are thought to protect i1ing ce s 0ro# 0ree radica s.
Chapter 4 4-

.adica Inhi*itors 2Continued3

% 6 radica chain reaction is 0ast and has #any eBother#ic steps that create #ore reacti1e radica s. % When an inhi*itor reacts <ith the radica , it creates a sta* e inter#ediate, and any 0urther reactions <i *e endother#ic and s o<.
Chapter 4 44

Car*on .eacti1e Inter#ediates

Chapter 4

44

Car*ocation Jtructure

% Car*on has 8 e ectrons, positi1e y charged. % Car*on is sp2 hy*ridi/ed <ith 1acant p or*ita .
Chapter 4 48

Car*ocation Jta*i ity

Chapter 4

47

Car*ocation Jta*i ity 2Continued3


% Jta*i i/ed *y a Fy su*stituents in t<o <ays'
1. Inductive effect' Lonation o0 e ectron density a ong the sig#a *onds. 2. Hyperconjugation' M1er ap o0 sig#a *onding or*ita s <ith e#pty p or*ita .

Chapter 4

4:

5ree .adica s

% 6 so e ectronEde0icient. % Jta*i i/ed *y a Fy su*stituents. % Mrder o0 sta*i ity' - S 2 S 1 S #ethy


Chapter 4 4;

Jta*i ity o0 Car*on .adica s

Chapter 4

40

Car*anions
% Eight e ectrons on car*on' 8 *onding p us one one pair. % Car*on has a negati1e charge. % Lesta*i i/ed *y a Fy su*stituents. % (ethy S1 S 2 S -
Chapter 4 41

Car*enes

% Car*on is neutra . % Racant p or*ita , so can *e e ectrophi ic. % Lone pair o0 e ectrons, so can *e nuc eophi ic.
Chapter 4 42

Kasicity o0 Car*anions

% 6 car*anion has a negati1e charge on its car*on ato#, #aFing it a #ore po<er0u *ase and a stronger nuc eophi e than an a#ine. % 6 car*anion is su00icient y *asic to re#o1e a proton 0ro# a##onia.
Chapter 4

4-

Car*enes as .eaction Inter#ediates

% % %

6 strong *ase can a*stract a proton 0ro# tri*ro#o#ethane 2C9Kr-3 to gi1e an inducti1e y sta*i i/ed car*anion. &his car*anion eBpe s *ro#ide ion to gi1e di*ro#ocar*ene. &he car*on ato# is sp2 hy*ridi/ed <ith trigona geo#etry. 6 car*ene has *oth a one pair o0 e ectrons and an e#pty p or*ita , so it can react as a nuc eophi e or as an e ectrophi e.
Chapter 4 44