Chemical Equilibrium

Page 1

RMUTL

Chemical Equilibrium Chollada Kulwat

2552

Chemical Equilibrium

7 "#$%&'(# (Chemical equilibrium) ภภภภภ! "#$ % & # ภ'( " ) ( ภ" *!( (+, ( -% (.+ / + ภ0) ภ) ภ, 1 (+, ( ) % % 1 1 ภ+ ภ2 ) 1 -% (.+ / +( ภ% % (+, ( "$ % ( % + ภ"&+) % % *ภภ" . "&*)1 &3ภ(&+, (+, ( !%" -% (.+ /) %*) ! % *ภ0 * 1 1 &*) . " $ *, * ภ. " 3% (equilibrium state) 0 3% 1 * (chemical equilibrium) 0) ภ3% 0 # . " 3% +, ภ%*) ! % " + 1 ( ) 2* !( +( ภ%*) ! % ภ(+, ( -% (.+ / & ภ+ +( ภ%*) ! % ภ-% (.+ / (+, ( 3% 1 * ภ* ภ3% ภ(dynamic equilibrium ) + ,-"#$%& . "&* ) " * +( ( F 1 &*) $ *1 1 &*) *1 + 1 &*) !%" *1 *1 &*) ( * ภG! 1 + 2+ H " +( " !%" % &*)#$ 20) %+ภ" . " 3% + *,

345 7.1 t1 = ',& 3- '7 "48+ ,-"#$%& 9:;<-' = 0$ ,8 "# >?17@;3- (;

7.1

"#$%&0$ #1ŕ¸

3%# ! +( ภภภ. " 3%&*) " * +( ' ภ& ภ+ +( ' ภภ%+ -%# +( ' 3&H ภ& ภ+

238

Chemical Equilibrium

7.1.1 "#$%&0$ #1ก# ก 3'5& A B5&;?&@$',& ก &*) " # . " 3% & # +( ' 3&H & ก+ I ) -%# +( ( F " 1 &*) $ 1 1 &*) 0) ก. ก 1% ก+ *ก %*) ! % ก , !( 1 " + 1 *ก %*) ! % (% % + 1 * ก ก , ( 2* !( +( ก ก ก & ก+ ก ก%+ & +, 7.1.2 "#$%&0$ #1ก<-? @;# "# >?1?8 ;D(; ! " *ก %*) ! % (% % !( ก %*) ! % & ก+ ก %*) ! % ก%+ & # " * +( 1 &*) 1 &3ก(+ # " "( 1 &*) กJ I1 + "( 1 &*) + +, 3 &*). " 3% " "( * +( 1 &*) !( ก'( " * +( 1 &*) " # . " 3% 0 ก' 7.1.3 ก3 FB"$;ก 3'ก1$"#$%&0$ #1ก 0) ก 3%&*) ก*) ก+ +( ก ก ก & +( ก ก ก + *,

! . " 3%#

345 7.2 B"$;+ ,-"#$%&G ' @#7@;@>?3 ก 3'ก1$5H1ก131A

R = +( ก ก ก t2 = % &*) " . " 3% I ) +( ก ก ก & ก+ ก ก%+ ก ก "2 # & +( ก ก ก !% ก' "2 # & +( 0) F " *ก $ 1 + ก A + B ⇔ C "! %+ก " 3%R 2 ก1 (+, ( (+ # (+ ) 0 -% (.+ / + (+ ก G( *,

239

Chemical Equilibrium

345 7.3 B"$;&>กQR-7@;"#$%&N$AS1< 3R < ก(, #'7 #7 7@;" 3?>M;? ?>,G$?>, :;

t = ',& 3- @A48G + ,-"#$%& 7.1.4 "#$%&0$ #1ก? @;'ก1$G 3- J> ก&> 0$ ก %*) ! % &*)-+ ก%+ ก %*) ! % &*) *&+, ก !%" ก ก%+ " &*) " ก . " 3% , "( " &*) *ก %*) ! % ! -+ ก%+ & +, $ , ก% # " * ก+ , ก' 1 ! ก%+ , ก %*) ! % ! -+ ก%+ !%" ก 3% ก !( ก - ก " ก %*) ! % ! -+ ก%+ ก 3% ก 7.1.5 "#$%&0$ #1ก" # 3L'ก1$7:M '@;0$ N$A@>?N #>?1 # " &*) %*) ! % ! -+ ก%+ " . " 3% R

+(R +( " ) ( ก ก 0 ก ก%+ 7.1.6 "#$%&0$ #1ก<-'ก1$7:M G 3- 5P$ ก &*)-+ ก%+ !%" ก # " S " ก 3% ก +, ก # " S " ก 3% $ ก " , # . $ " S " * 3% !( ก " , # . $ " S " * 3% ก , 7>M ?@ G ก 3 $"@ ก 3'ก1$"#$%&0$ #1ก

240

Chemical Equilibrium

( 2 ก ก %*) ! % +, -+ ก%+ 0 -+ ก%+ R ก & &+, ก (#$ (+, ( & ก ก+ ) !%" ก ก%+ (#$ -% (.+ /& ก ก+ ) ก +, -+ ก%+ " *R ก ก 3% +, ( 2 1 !( %"(+ 1 1 &*) ! ก %+ # . " 3% 1 + 1 &*) ! ก %+ 3%

7.2

53-'+ 7@;"#$%&0$ #1ก ! ( %+ก "ก %*) ! % + *, 7.2.1 "#$%&3- ,8 ;"L - !ก − 3% ก % % $ H2O (s) ⇔ H2O (l) − 3% ก ก $ C2H5OH (l) ⇔ C2H5OH (g) − 3% ก " $ I2 (s) ⇔ I2 (g) 7.2.2 "#$%&7@;" 3&-& A !ก − 3% ก !(ก(+ I ) ก , ก+ ก %"% %'กR( %( # , $ CH3COOH + H2O ⇔ CH3COO- + H3O+ − 3% ก %"% I ) ก , ก+ ก %"% %'กR( %(!ก !%" %'กR( %( # , 0 # (+ & %"% 0) F &+, *,. " 3% " ก , 0) %"% ) (+ $ NaCl (s) ⇔ Na+ (aq) + Cl- (aq) !%" C6H12O6 (s) ⇔ C6H12O6 (aq) 7.2.3 "#$%&< ก5H1ก131A '(# $

Fe 2+ (aq) + Ag + (aq) ⇔ Fe 3+ (aq) + Ag (s) 2H 2 (g) + O 2 (g) ⇔ 2H 2 O (g) CaCO 3 (s) ⇔ CaO (s) + CO 2 (g) ?>,@A8 ; 7.1 ก %*) ! % ( *, " # # . " 3% ก ก. , ! ' # !ก &*) *` S . , # ก "( ก , &*) *a * 1. , $0) &*) *-% ก , ( % ก . , &*)ก %+ 0 # ก . 3% ก ก% H2O (g) ⇔ H2O 1. 3% ก %"% , ( % ( ! ' ) ⇔ , ( % ( %"% ) 241

Chemical Equilibrium

ก. !%" . #$ 3%

?>,@A8 ; 7.2 ก %*) ! % ( *, # ก %*) ! % ! -+ ก%+ ก. %"% ก "I ( ก# , . %"% , ( % 1 ก + # , ก ก 2 1. ก # 1 !ก -% ก I2 # % & % . ก %*) ! % &# & R ( ก. . 1. .

-+ ก%+ CH3COOH + H2O ⇔ CH3COO- + H3O+ -+ ก%+ *!( ก -+ ก%+ *!( ก -+ ก%+ Hg (l) ⇔ Hg (g)

?>,@A8 ; 7.3 ( ก ก ก ( *, *. " 3% ก , 0 "& 2Fe3+(aq) + 2I-(aq) ⇔ 2Fe2+(aq) + I2(aq) 1. & ก -+ ก%+ R ! 2 ( ก. & * ก #$ Fe3+ & ก ก+ I- !% ( Fe2+ !%" I2 Fe2+ & %"% K3Fe(CN)6 " ("ก * , Fe2+ + K+ + Fe(CN)63- ⇔ KFe[Fe(CN)]6 I2 & R #$ , ! e " ("ก * , -%ก & * Fe2+ !%" I2 ก'! * ก . & * ก ก%+ R #$ Fe2+ & ก ก+ I2 !% ( Fe3+

%"% NH4SCN I ) " *! Fe3+ + SCN- ⇔ FeSCN2+ *! ก & -%&+, ก !%" " 3 *ก %*) ! % &*)-+ ก%+ I ) " & +, ( !( ก & 2 +, # +, ) 10 ก 0 ก ก ก'! -+ ก%+ " " ก 3% "( & +, (

242

Chemical Equilibrium

2. " -+ ก%+ "& 1 Fe3+ , I- , Fe2+ !%" I2 1 &*) 0 1 1 &*) ! ก %+ 3% 1 &*)ก'! + 3% B TUก >$ 7.1 - %"% Ba(NO3)2 ก+ %"% Na2SO4 ก+ " ก " # &*) " # . " 3% ก. Ba(NO3)2 (aq) ⇔ Ba2+(aq) + 2NO3- (aq) . Na2SO4 (aq) ⇔ 2Na+ (aq) + SO42- (aq) 1. NaNO3 (aq) ⇔ Na+ (aq) + NO3- (aq) . BaSO4 (aq) ⇔ Ba2+ (aq) + SO42- (aq) . Ba(NO3)2 (aq) + Na2SO4 (aq) ⇔ BaSO4 (aq) + 2NaNO3 (aq)

7.3

&>ก7@;'&@V '?@&1'A3W

ก : j 0) " &*) # . " 3% ก ก R ก %*) ! % k + &*) *-%( . " 3% " " ก ก %*) ! % # & & &*) "% -% ก ก +, 20) # . " 3% *ก1 +, ) l %+ก % $ ( % #$ H & & ก %*) ! % ก 0) *ก ก 3% " $ 0) 2 ) 1 " " ก ก # & & &*) "& # 1 &*) 2 ) , +, % % 0) 2 ) 1 + # !ก " " " ก ก # & & &*)& # 1 + % % + +, & # & & & ก %*) ! % " & # & ก " ก 0 ก%+ 0 & # & -% (.+ / " 2 ) , 0 % %

7.4

5X<<>A # J&?8@+ ,-"#$%& !ก 1 1 + !%" 3 .

7.4.1 J&7@;(, #'7 #7 ?8@+ ,-"#$%& # "&*) " ก %+ # . " 3% ก 2 ) 1 # ) # " "& # * . " 3% ( %+ก % $ ( " " + (+ # ก%+ 3%# # & & &*)% 1 +, # & ( ก+ % 1 # " " " + (+ # ก%+ 3%# # & & &*) 2 ) 1 +, 2 (+ " Fe3+ , SCN-, FeSCN2+ 0) 2 ) !%"% 1 ( F " *ก + (+ # ก%+ 3%# + *, 243

Chemical Equilibrium

2 ) 2 ) % % 2 ) %

Fe3+ SCNFe3+ SCNFeSCN2+ FeSCN2+

Fe3+ + SCN↑ ↓ ↓ ↑ ↓ ↑ ↑ ↓ ↑ ↑ ↓ ↓

⇔ FeSCN2+ → ↑ → ↑ ← ↓ ← ↓ & & % ก ← ↑ → ↓

↑ = 2 ) , ↓ = % %

7.4.2 J&7@;(, #$> ?8@+ ,-"#$%& 1 + # &*) *, 1 + &+, " #$ 1 + !กJ $ # $ ) ก 2 ) 1 + ก 2 ) 1 + # !ก " &3ก(+ # " " *1 + 2 ) , & F ก+ 1 + *1 + 2+ Hก+ ( R %!%"1 + *, 1 P∝ ,P∝n ,P∝C V P = 1 + " , V = ( " n = R % " , C = 1 ก %*) ! % 1 + " "& # " + (+ # ก%+ 3%# R ก ก ก 0 ก%+ ก' ก ! ก " # $ 7.4.2.1 3- (, #$> 0#8# J&?8@+ ,-"#$%& * 2 " 10 " &*) *!กJ !%" " &*) R % !กJ &*) (+, ( & ก+ R % !กJ &*) -% (.+ / ก ( *, (+ " &*)1 + *-%( . " 3%

Fe 3+ (aq) + SCN − (aq) ⇔ FeSCN 2+ (aq) Ag + (aq) + Fe 2+ (aq) ⇔ Ag (s) + Fe 3+ (aq) H 2 (g) + Cl 2 (g) ⇔ 2HCl (g)

244

Chemical Equilibrium

Fe (s) + 4H 2 O (g) ⇔ Fe 3 O 4 (s) + 4H 2 (g)

7.4.2.2 3- (, #$> # J&?8@+ ,-"#$%& !ก " &*) *!กJ !%" R % !กJ &*) (+, ( !%"-% (.+ / "( & ก+ $ 2 NO 2 (g) ⇔ N 2 O 4 (g) H 2 O (l) + CO 2 (g) ⇔ H 2 CO 3 (aq) Cu (s) + 4HNO 3 (aq) ⇔ Cu(NO 3 ) 2 (aq) + 2NO 2 (g) + 2H 2 O (l) 7.4.2.3 J&7@;ก 3'5& A B5&;(, #$> ?8@+ ,-"#$%& + " &*) R % กJ I&*) (+, ( & ก+ -% (.+ / %ก & '(" ก ) '(" # ( ก* + & # !

'("ก *" , '( - # ก& .&ก& &# ' &/ ) - * ' ก *" 0" * .&ก& &# ก& ' &/ & ) - 1 $ 2 ) 1 + # !ก " ( *, "& # ก ก ก , 2 NO 2 (g) ⇔ N 2 O 4 (g) CO 2 (g) + H 2 O (l) ⇔ H 2 CO 3 (aq) 2NO (g) + 2CO (g) ⇔ N 2 (g) + 2CO 2 (g) 0) ก R %&*) !กJ -% (.+ / ก (+, ( ก ก R % " "% % I ) -%& # 1 + " % % ( P ∝ n ) + +, ก 2 ) 1 + & # ก ก 2 ) , 20) +ก . " 3% " ( *, 2 ) 1 + # !ก " "& # ก ก ก%+ ก , PCl 5 (g) ⇔ PCl 3 (g) + Cl 2 (g) C (s) + H 2 O (g) ⇔ CO (g) + H 2 (g) CH 4 (g) + 2H 2S (g) ⇔ CS 2 (g) + 4H 2 (g) 0) ก R % (+, ( ก -% (.+ / ก ก ก ก%+ & # R % " % % -%# 1 + " % % !%"ก%+ . " 3%# 53-'+ 7@;5H1ก131A G B;87@;S&>;; ! 2 " .& 10 245

Chemical Equilibrium

1. ภ1 1 2. ภ1 # 0) 3% 1 *I ) *&+, ภ!%" ภ%+ ภภI ) * ภ# " !%" ŕ¸

ภ%+ , " $

ภภI ) * ภ, " !%" ŕ¸

ภ%+ # " $

ภ3ภY $7 @#4&'ภA,ภ> S&>;; 7@;5H1ภ131A R & "ภ%# R ( 0 R ภ' (+ ภภ%# R ( $ 2NO + 2CO ⇔ N2 + 2CO2 ภ1 1 C(s) + H2O(g) ⇔ CO(g) + H2(g) ภ1 + ภภ%# & "& % H* ?>,@A8 ;?8@05 M'5Z ภ3'5& A B5&;53-'+ ( A(, #3 @ I 2NO2 (g) ⇔ N2O4 (g) + heat II 2P2O3 (g) ⇔ P4O6 (g) ∆H = -230 III 2SO2 (g) + O2(g) ⇔ 2SO3 (g) ∆H < 0 IV N2 (g) + 3H2(g) ⇔ 2NH3 (g) + 92 kJ ?>,@A8 ;?8@05 M'5Z ภ3'5& A B5&;53-'+ $4$(, #3 @ I N2 (g) + O2(g) + heat ⇔ 2NO (g)

246

Chemical Equilibrium

II NaCl (s) ⇔ Na+ (aq) + Cl-(aq) ∆H > 0 III PCl5 (g) ⇔ PCl3 (g) + Cl2(g) - 92.9 kJ IV C (!ก G() ⇔ C ( 2$ ) ∆H = +1.9 kJ 7.4.3 J&7@;@%R +4#1?8@"+ ,-"#$%& 0) 2 ) 3 . # !ก " "& # * . " 3%( %+ก % $ ( % " " + (+ # ก%+ 3%# # & & &*)% 3 . " I ) ก'10 ก ก 1 !%"# & ( ก+ 0) % 3 . " " ก ก 1 1 2 ก(+ ก 1 1 !%" ก 1 ( *,

" ' ก 2 ) 3 . "& # " ก ก 1 I ) " ก 0 ก%+ ก' ( !( $ ก + +, ก 2 -% 3 . ( . " 3% ( & ก ก +, " .& 0 1 1 !% #$ %+ก % $ ( % 2 ( # ก *&*)R & ก %# F&*) "#$ (+ ก +, 0 1 1 ! R & ( ก # 2 ก*) ก+ -% 3 . ( . " 3% "3%5J&7@;(, #'7 #7 (, #$> B&-@%R +4#1?8@+ ,-"#$%& j 2 ) 1 # ) # ก. -% 1 ( . " 3% " "& # ก ก # & & &*) "% 1 +, l . -% 1 + ( . " 3% j 2 ) 1 + # !ก " " ก ก # & & &*) "% R % " % l 1. -% 3 . ( . " 3% j 2 ) 3 . # !ก " " ก ก 1 l

247

Chemical Equilibrium

7.5

ภ3S1< 3R 5X<<>A # J&?8@+ ,-"#$%&G B;87@;ภ3 F

0) *ภภ. " 3% ภ, " " + (+ # ภ%+ . " 3%# I ) "R ภภภ0 ภภ%+ ภ+ (+ # ภ%+ . " 3% # *, "& # 1 !( %"$ %*) ! % I ) * ภG ! ภ%*) ! % $ 2NO2 (g) ⇔ N2O4 (g) + heat ) ( ภNO2 ) & # % (+ . " 3% "2 1 NO2 !%" N2O4 *1 1 &*) ภ. " 3%R ภ( N2O4 % ) ( %+ภ% $ ( % " ภภภ%+ 20) +ภ. " 3% + +, NO2 " ภ, # "&*) N2O4 "% % %'ภ!%"# &*) 3 "1 &*) 0) 3%# &+, *,1 NO2 !%" N2O4 " & ภ+ &*). " 3%! ภ2NO2 (g) ⇔ N2O4 (g) ↑ â†? ↑ 2 ) N2O4 %+ภ"ภG! ภ%*) ! % 1 20) ภ%+ 3%# " + *,

345 7.4 ',& ?>M;B?8 t0 L:; t1 3- ภY &>;@A48G + ,-"#$%&

% t1 ) ( N2O4 & # * 3% I ) " " ) + # 3%# &*) t2 R

N2O4 % % %'ภ!%" NO2 2 ) , t3 3%#

248

Chemical Equilibrium

ก3R '5& A B5&;(, #$> 3\@@%R +4#1ก' * ก G $ * ก+ ก. 0) 2 ) 1 + # " 2NO2 (g) ⇔ ↓ →

N2O4 (g) ↑

1

2NO2 (g) ⇔

N2O4 (g)

. 0) 2 ) 3 . # !ก "

↑

7.6

←

↓

ก 3'5& A B5&;?Y B 8;7@;"#$%&

0) *ก ก . " 3% ( ! 3% " %*) & & ก %*) ( ! ก'10 & & ก + (+ # ก%+ 3%# $ " + (+ # ก%+ 3%R ก ก ( ! 3% " %0) กI !%" " + (+ # ก%+ 3%R ก ก ก%+ ( ! 3% " %0) ก I

Fe2+ (aq) + Ag+ (aq) ⇔ Fe3+ (aq) + Ag (s) 2 ) Fe2+ ↑ ↓ → ↑ ↑ ( ! 3% %0) กI 2 " ก ก

249

Chemical Equilibrium

2 ) 1 +

2NH3 (g) ↑

⇔ N2 (g) + 3H2 (g) ← ↓ ↓

( ! 3% %0) ก I 2 " ก ก ก%+

7.7

ก 3GV &>ก7@;'&@V '?@&1'A3WG @%?" ก33#

20) # -% (.+ / ก&*) 3 # % &*) 3 ก % ( &3 $ ก. ก -% ( NH3 ก N2 !%" H2 1

N2 (g) + 3H2 (g) ⇔ 2NH3 (g) + heat % T ↓ ↓ → ↑ 2 ) 1 + ↓ ↓ → ↑ ก #$ 3 . () !%"1 + "& # NH3 ก , # "&*) NH3 ก "1

1 I ) & ก+ ก 2 ) 3 . # !ก " !%" "& # NH3 % % + +, # & +( #$ 3 . &*)() 0 ก ก% 10 #$ 3 . " 500OC 1 + " 350 atm !%"#$ Fe (+ ก . ก -% (ก H2SO4 I ) ( ( * SO3 ก 1

2SO2 (g) + O2 (g) ⇔ 2SO3 % T 2 ) 1 +

↓ ↓

↓ ↓

→ →

↑ ↑

( #$ 3 . () !%"1 + " SO3 ก

7.8

?>,'38;5H1ก131A ก> + ,-"#$%&

ก +, + 3% (+ ก "$ & # . " 3% ' , !%" ก +, ก %+ # . " 3% (+ ก " *-%( . " 3% !( ก'( (+ ก * # ก & # -% (.+ / 2 ) 0 % "#$ (+ ก 0 " -% (.+ / & ก+ ก &*)(+ ก & # ( ! 3% %*) ก' 2 " (+ ก "% 2%+ ก "(3 &+, ก !%" ก ก%+ 2 Fก+

250

Chemical Equilibrium

?>,@A8 ; 7.4 ก ก ( *, Fe2+ (aq) + Ag+ (aq) ⇔ Fe3+ (aq) + Ag (s) ( ก # ("ก %"% ก , 1 " 2 ) 0 % 1 # ( %+ก % $ ( % Ag "% % 0) " ก ก ก%+ I ) & R 2 ) Fe3+ % Fe2+ 0 % Ag+

2 ) Fe3+ % Fe2+ % Ag+

Fe2+ + Ag+ ⇔ Fe3+ + Ag ↑ ↑ ←↑ ↓ ↓ ↑ ←↓ ↓ ↑ ↓ ←↓ ↓

?>,@A8 ; 7.5 ก ก %*) ! % # + *, 2Z(s) + Y2(g) ⇔ 2ZY(g) + energy 2 ) 1 + R % ( !( # 3 . 1 &*) " " * 3% !%" + (+ ก%+ 3%# *ก1 +, ) ก. # $ % &*) " ก %+ 3%# +( ก ก ก " 0 () ก +( ก ก ก ก%+ . 2 ) 1 + !%" " 3% *ก 1 ZY " %*) ! % ก. ก ก R %&*) !กJ -% (.+ / กก (+, ( + +, 0) 2 ) 1 + # " "& # * 3% ( %+ก % $ ( % " " + (+ # ก%+ 3%# # & & &*) "% 1 + 0 # & & &*) "% R %&*) !กJ I ) ก ก ก ก%+ 2Z(s) + Y2(g) ⇔ 2ZY(g) 2 ) 1 + ↑ ↑ ← ↓

251

Chemical Equilibrium

ก &*) " ก ก ก%+ 20) 3%# ! +( ก ก ก ก%+ กก +( ก ก ก . ก 2 ) 1 + & # " ก ก ก%+ 20) +ก . " 3% + +, ZY I ) -% (.+ / % % B TUก >$ 7.2 1. ก ( *, # &*)ก 2 ) 1 + # !ก " & # " + (+ ก%+ 3% # # & & &*) 2 ) -% (.+ / ก. C(s) + O2(g) ⇔ CO2(g) . CO(g) + 2H2(g) ⇔ CH3OH(g) 1. C2H6(g) ⇔ C2H4(g) + H2(g) . Pb2+ (aq) + H2S(aq) ⇔ PbS(s) + 2H+(aq) . 2NO(g) + 2CO(g) ⇔ N2(g) + 2CO2(g) a. 3Fe(s) + 4H2O(g) ⇔ Fe2O3(s) + 4H2(g) 2. ก. . 1. .

ก %*) ! % ( *, # &*) ก ก ก%+ 0) 2 ) 3 . N2 (g) + 2CO (g) + heat ⇔ 2NO(g) + 2CO (g) H2O (l) + CO2 (g) ⇔ H2CO3 (aq) 2SO2 (g) + O2 (g) ⇔ 2SO3 (g) ∆H < 0 PCl5 (g) ⇔ PCl3 (g) + Cl2 (g) ∆H = +92.9 kJ

3.

ก ก ( *, 4HCl(g) + O2(g) ⇔ 2H2O(g) + 2Cl2(g) + heat ( ก # !กJ Cl2 2 ) ก , "&

4.

ก ก ( *, 2Fe(s) + 4H2O(g) ⇔ Fe3O4(s) + 4H2(g) ( ก # ( ! 3% %0) ก I "( &

5. + *,

ก ก ( *, A(g) + B(g) ⇔ C(g) *%+ก "ก ก

252

Chemical Equilibrium

2 ) 3 . # !ก " " *ก %*) ! %

6.

ก ก A(g) + B(g) ⇔ C(g) 0) + 1 # $ % ( F ก+ !% * ก G -% + *,

ก. . 1. . 7.

&*) % t1 " ก ก k + ) k + +, 10 " ก 2 ) 3 . # !ก " ก 2 ) 1 + # !ก " ก 2 ) 1 &+, ก , , 1 PCl5 % (+ + *, PCl5 (g) ⇔ PCl3 (g) + Cl2(g) กก & % +( ก % (+ PCl5 R + %&*) %0 ก -% + *, @%R +4#1 (OC) 200 250 300

#,& PCl5 ' &\@ (ก3>#) 5.0 6.5 8.0

ก. ก % (+ PCl5 2 ) , 0 % % 0) 3 . 2 ) , . ก % (+ PCl5 " .& 0 1 1

253

Chemical Equilibrium

8.

ก. . 1. . 9.

A !%" B & ก ก+ + *, aA (g) + bB (g) ⇔ cC (g) กก & % 2 0) 3 . 2 ) , C " 2 ) , !( 0) 1 + 2 ) , C " % % ก. ก %*) ! % *, 0 1 1 . 1 + 2+ H " a , b !%" c

10. ก. . 1. . 11.

ก ก %*) ! % ( F # + ( *, AgCl (s) ⇔ Ag+ + Cl- (aq) !%" Ag+ (aq) + 2NH3 (aq) ⇔ Ag(NH3)2+ (aq) AgCl %"% # , &*) * ( F- # &*) AgCl %"% ก&*) 3 ( ( (+ & %"% % AgCl !%" 3 . &*)#$ 1 &*) %"% # , &*) *ก ก%0 - %'ก

%"% # , &*) * NH3 - %'ก

%"% # , &*) * ก%0 NaNO3 - %'ก

*1 ( &*) ก( 2 " AgCl %"% ,

ก ก ( *, # &*)1 + *-%( . " 3% Ag+ (aq) + 2NH3 (aq) ⇔ Ag(NH3)2+ (aq) C (s) + O2 (g) ⇔ CO2 (g) 3Fe (s) + 4H2O (g) ⇔ Fe2O3 (s) + 4H2 (g) C2H4 (g) + H2 (g) ⇔ C2H6 (g)

ก ( *, # &*)ก 2 ) 1 + " *-%( ก+ ก 2 ) 3 . ก. 2SO2 (g) + O2 (g) ⇔ 2SO3 (g) + heat . N2 (g) + 2H2 (g) ⇔ N2H4 (g) ∆H > 0 1. Fe3+ (aq) + Ag (s) ⇔ Fe2+ (aq) + Ag+ (aq)

254

Chemical Equilibrium

7.9

(8 (; 7@;"#$%&

#$ +z%+ภ&+) aKb 0) " # . " 3% 1 &3ภ(+ # " " *1 1 &*) * *" *" * & 23! $ ( ( *" *" * $ " $ ( ( 4 #, . " 3%

*1 1 &*) * ภ+( + ภ% 2 ภaA + bB ⇔ cC + dD 1 A a R % & ภ2 *ภ+ B b R % C c R % !%" D d R % 0) a , b , c , d (+ % &*)& # ภ3% 1 + 2+ H 1 (+, ( !%" # &*). " 3% + *,

[C]c [D] d " 1 1 &*) 3% = K= a b [A] [B] [HCl] 2 $ H2 (g) + Cl2 (g) ⇔ 2HCl (g) , K = [H 2 ][Cl 2 ]

7.10 (8 (; 7@;"#$%&G ' @#7@;(, #$> #$ +z%+ภKP *%+ภ" 0 ภ+ # & 1 2* !( %*) ภ1 1 + KP #$ a2 " " &*) !ภJ & +, $

PB3 2A (g) ⇔ 3B (g) ; K P = 2 PA P #$ !& 1 + # & * ภ+ [ ] #$ !& 1 KP !%" KC ( 0 K) *1 + 2+ Hภ+ + *,

K P = K(RT) ∆n ∆n = R %-% (.+ / (ภJ I) - R % (+, ( (!ภJ ) 255

Chemical Equilibrium

7.11 (8 K ภ> "L -7@;" 3 1 K "2 a2 " %"% !%"!ภJ & +, ! ' 0 % &*) 3&H } 0 *1 1 &*) ( ! # 1 K $ CaCO3 (s) ⇔ CaO (s) + CO2 (g) ; K = [CO2]

[NH 3 ][OH - ] + NH 4 (aq) + H 2 O (l) ⇔ NH 3 (aq) + OH (aq) ; K = [NH +4 ]

CaCO3 !%" CaO ! ' H2O % ( ! # 1 K 8,A7@;(, #'7 #7 B&-(, #$> # 1 K 1 ( R %/% ( & +, " 0) F !%" 1 + "#$ atm 7.11.1 (8 K 0#87:M ภ> (, #'7 #7 B&-(, #$> ! 1 " %*) ! % 0 1 + " %*) ! % 1 K " %*) ! % &*). " 3%!( %"1 +, 1 !( %"$ # " " & ภ+ !( 1 K "( & ภ+ $ # ภPCl5(g) ⇔ PCl3(g) + Cl2(g) 1 1 &*) &*). " 3% (1) 0.45 0.15 0.15 K = 0.05 &*). " 3% (2) 0.20 0.10 0.10 K = 0.05 ! 1 &*). " 3%&+, & ภ+ !( 1 K & ภ+ 7.11.2 (8 K 7:M @A48ภ> @%R +4#1 3 . %*) ! % 1 K ภ"( %*) ! % !%" 3 . 1 &*) 1 K "1 &*) ภ&*) K " 2 ) 0 % ภ' , ภ+ $ ภภ3'5& A B5&;@%R +4#1 3 . 2 ) , 3 . % %

5H1ภ131A ( A(, #3 @ K % % K 2 ) ,

7.11.3 ภ3 FB"$;ภ3'5& A B5&;7@; K ภ> @%R +4#1

256

5H1ภ131A $4$(, #3 @ K 2 ) , K % %

Chemical Equilibrium

&+, ภ1 !%" 1 1 ! 1 + 2+ H " K ภ+ 3 . % ! + *,

ภ. ภ1

. ภ1 1

? 3 ; 7.1

?>,@A8 ;7@;(, #">#S> cW3- ,8 ; K ภ> @%R +4#1

5H1ภ131A PCl5 (g) ⇔ PCl3 (g) + Cl2 (g) ∆H = 92.9 kJ 2SO2 (g) + O2 (g) ⇔ 2SO3 (g) ∆H = -196.7 kJ

@%R +4#1 (OC) 200 250 500 600

K 0.0049 0.050 1.5 x 105 5.0 x 103

7 @(,3<Y ภ. 3 . ภภ"& # " * . " 3%!% + & # 1 K %*) ! %

. 1 !%"1 + & # " * . " 3% !( & # 1 K %*) ! % # A' ?%

257

Chemical Equilibrium

ก. 1 K #$ & & & ก ก ก (1 K ก ก -% (.+ / ก ก . 1 K ก +( ก ก ก ( ก!1 -% (.+ / ก ก 0 !( ก ก ก ' 0 $ )

7.12 (8 (; "#$%&7@;ก 3&-& A #$ +z%+ก K 0 Ksp 3% ก %"% ก%0 &*)%"% # ,

ก $ Ksp AgCl !%" BaSO4 (

A x B y (s) ⇔ xA y + (aq) + yB x- (aq) ; K sp = [A y + ]x [B x- ] y

AgCl (s) ⇔ Ag + (aq) + Cl - (aq) ; K sp = [Ag + ][Cl - ] CaF2 (s) ⇔ Ca 2+ (aq) + 2F - (aq) ; K sp = [Ca 2+ ][F - ]2 Ksp GV กY $(, #" # 3L7@;ก 3&-& A ก%0 &*) * Ksp ก "%"% , *ก ก%0 &*) * Ksp $ &*) 25OC MgCO3 * Ksp = 1.0 x 10-5 !%" CaCO3 * Ksp = 4.8 x 10-9 ! MgCO3 %"% , กก CaCO3 ก ก "#$ Ksp ก 1 # ก %"% ก%0 !% + #$ ! ก &*) - ก+ ก กก+ R + ก (ก("ก ก%0 &*) * Ksp

?>,@A8 ; 7.6 * 1 1 &*) 3% ก ( *, ก. Cu (s) + 2Ag+ (aq) ⇔ Cu2+ (aq) + 2Ag (s) . PbI2 (s) ⇔ Pb2+ (aq) + 2I- (aq) 1. N2 (g) + O2 (g) ⇔ 2NO (g)

[Cu 2+ ] ก. K = + 2 [Ag ] . K = [Pb 2+ ][I - ] 2 [NO] 2 1. K = [N 2 ][O 2 ] 258

Chemical Equilibrium

?>,@A8 ; 7.7 ภภA + B ⇔ C *!- . 2! ภภ+ *,

ภภ& % 1 1 &*) 3%&*) 3 . ( F ภ-% + *, 3 . (OC) K

T1 0.05

T2 0.09

T3 0.23

* % + 3 . ภ() ภภG ! !- . 2 ภภ! ภ%*) ! % " .& 1 I ) 0) 3 . 2 ) K " 2 ) , ภR & 0) %* ) T1 → T3 1 K 2 ) , ( % + ∴ % + 3 . T1 < T2 < T3 B TUภ>$ 7.3 1. ภภA + 2B ⇔ C 0) ) ( #$ A 2.0 mol/l , B 3.0 mol/l %+ ภภ. " 3% 1 B * ภG ภ-% + *,

259

Chemical Equilibrium

1 1 1 &*) 3%

2.

ภภCOCl2 (g) ⇔ CO (g) + Cl2 (g) K = 1.2 x 10-5 0) COCl2 0.5 mol/l # % # . $ "&*) * Cl2 !% 0.2 mol/l 1 1 COCl2 , CO !%" Cl2 &*). " 3%

3.

ภ# Ksp AgCl 1.8 x 10-10 1 ภ%"% AgCl # , ภ+ /% (

4.

ภKsp BaSO4 1.5 Ă— 10-9 0) BaSO4 ) %"% # %"% &*) * SO42- !% 0.01 mol/l 0) . " 3% " Ba2+ ภ*) R %/% (

5.

&*) 25OC %"% ) (+ CaF2 # , *1 0.0068 ภ+ ( , 250 cm3 1 Ksp CaF2 &*) 25OC

260

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