Bài Tập Hóa Học Đại Cương & Hóa Lý Cơ Sở - Lâm Ngọc Thiềm
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Transcript of Bài Tập Hóa Học Đại Cương & Hóa Lý Cơ Sở - Lâm Ngọc Thiềm
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LM NG C THIM (Ch bin)
TR N HIP H
HABI TPm
HC I CNm H
H a h c l t h u y t c s )
(In ln th II)
f ?RfNGSABpCGVHMN I TRuHGs TM H ^S T n t i j \
IPHHC? C r O T P H H PHHC? CrO T P H H
ZZlM4M~lNH XUT BN I H C QU.C GIA H NI
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L i N i U
Thng thng gia l thuyt v bi tppj ca mt mn hc bao gi cng c gn kt cht ch vi nhau. lm c cc dng bi tp ngi hc phi hiu k thuyt v bit cch vn dng n vo tng trng hp c th, k c cc php chuyn i n v tnh ln th thut gii ton.
Cun B i tp ha hc a i cng (Ha hoc l thuytc s) nhm p ng cc yu cu ny.
Sch gm 17 chng gm hu ht cc vn l thuyt c
s ca ha hc v c trnh by di dng bi tp. mi
chng chng ti i phn lm 3 phn nh:
A. Tm tt l thuyt
B. Bi tp c li gii
c. Bi tp cha c li gii
Trong chng cui cng ca sch chng ti trch dn mt s thi tuyn sinh v p n ca mn hc ny nhm gip cho bn c hnh dung v mt thi tng hp v cch gii quyt n.
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Ni dung cun bi tp c bin son theo ng chng trnh chun c hi ng chuyn ngnh i hc Quc gm H Ni thng qua.
Cc tc gi v Nh xut bn rt mong nhn c nhng kin ng gp ca c gi ln xut bn sau c hon thin hn.
Cc tc gi
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MC LC
Trang
Khi nim v th nguyn, n v......................... 7
Chng I. Mt s'khi nim chung........... :.................... 13
Chng L ^ Nguyn l I ca nhit ng lc hc. Nhitha hc.-T......................................................... 25
Chng II. ^ Nguyn l II ca nhit ng lc hX-...45
Chng IV. 't Cn bng ha hc.-v........................................... 59
Chng V. y Dung dch....................................................... 83
Chng VI. J ng ha hc.................................................... 119Chng VII. V^ in ha hc. -y................ ............ ................... 139
y* Chng VIII. Ht nhn nguyn t ....................................... 161
Chng IX. Cu to nguyn t theo quan im c hclng t ............................................................. 171
Chng X. Nguyn t hidro............................................. 179
Chng XI. Nguyn t nhiu electron......................... 193
ChngXII. H thng tun hon cc nguyn t'ha hc.. 203
' Chng XZ7J/cc khi nim chung v lin kt thuyt VB. 215
Chng X iv^y Thuyt MO v lin kt............................... . 240
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Chng XV. Lin kt gia cc phn t v trong phccht....................................... ............................ 263
Chng XVI. Lin kt ha hc trong tinh th...................... 279
Chng XVII. Mt s thi v hng n gii mn hahc l thuyt..................................................... 297
Phc 370
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KHI NIM V TH NGUYN, N V
I. T h nguyn. Cc i lng (vt l) cn o thng c
vit di dng mt biu thc ton hc v c biu din bng
mt phng trnh th nguyn.-Phng trnh th nguyn c th
xem nh mt biu thc ton v c biu din bng cc i
lng c s di dng mt tch s'
Tt c cc th nguyn ca nhng i lng cn o trong co'
hc u xut pht t 3 i lng c s l: Chiu di: L; khi
lng: M; thi gian: T. Cc i lng ny lp thnh h Li.M.T.
J 1 f _ on ng L !V d th nguyn cua tc [v] = v ~ = = L. I .
Th nguyn ca lc [F] = khi lng X gia tc = M.L.T2
Th nguyn ca cng (nng lng) [A] = lc X on ng
Nh vy th nguyn khng ch r cc i lng cn o mt n v c th no.
Mt i lng cn xc nh m cc th nguyn ca chng u b trit tiu s dn ti i lng khng th nguyn
II. n v. Khi ngi ta tin hnh o mt; i lng no
thi gian T
Th nguyn ca L tc [a] =thi gian T
= M.L.T' 2 X L = M.IT"2
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tc l mun so snh i lng vi i lng cng loi ly lm chun so snh .gi l n v o .
Cc n v o c xc nh bi mu chun lu gi ti vin
cn o quc t. V d mt l n v o chiu di.
ln ca mt i lng vt l c th m theo qui c ly
gi tr bng s l 1 c gi l n v ca i lng vt l . V
d: mt, kilogam. Tp hp cc n v lm thanh mt h n v.
c mt s" h n v thng dng nh: h VKS (mt, kilogam,
giy); h CGS (xngtimt,'gam, giy)... /
Trong thc t, do thi quen, tng a phng, ung vng
'inh th, ngay c tng quc gia ngi ta s dng nhng n v
r t khc nhau cho cng mt i lng o.
V d n v chung cho chiu di l it, song ngi Anh
l dng Ins (Inch), pht (foot), trong khi ngi Vit li dng
trng, gang. tc...
R rng cch dng ny gy kh khn trong giao lu
quc t. V vy cn c mt n v quc t chun.
III. H n v SI. Nhn thy s bt li v vic s dng h
n v ty tin nn vo thng 10-1960 ti Hi ngh ln th XI v
cn o quc t hp Paris, cc nh khoa hc i n thng
nht cn xy dng mt h thng n v chung quc t. l n
v SI (Vit t t t ch Php - Systme International)
Di y chng ti lc ghi mt s ch dn quan trng nht
thuc h SI c lin quan n vic s dng cho cc bi tp ha i
cng.
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1III.l. H n v c s
7 n v chnh thuc h SI
N Tn i lng n v K hiu
Ting Vit Ting Anh
1 Chiu di met metre m
2 Thi gian giy second s
3 Khi lng kilgam kilogram kg
4 Lng ch't mo mol mo
5 Nhit ken vin Kelvin K
6 Cng dng in Ampe Ampere A
7 Cng nh sng nn Cndela cd
IL2. Mt s" n v SI dn xut hay dng
T 7 n v c s nu trn ngi ta cn c th nh ngha mt s' n v dn xut thng dung trong h SI. V d:
- n v lc. chnh l lc tc dng ln mt vt c khi lng lkg gy ra mt gia tc bng lm/s2. n v dn xut thu c y gi l Newton (N)
IN = lkg.m.s"2
- n v p sut. Trong n v SI, p suai Pascal -(Pa).
p sut thu c l do c tc dng ln 1 n v din tch.
lPa = lc/din tch = = kg ms"2 /m 2 = kgm- 1s- 2m
Di y l mt s n v dn xut hay dng
N Tn i n v K Theo
lng Ting Vit
TingAnh
hiu nh ngha
1 Lc Niutn Newton N kgm"2
2 p sut Patean Pascal P kgm ^s^N/m 2)
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3 Nng lng Jun Joule J kgmV"
4 Cng sut Ot Watt w kgm"s_1(i /s)5 in tch Culng Coulomb c ' As6 in th Vn Volt V _J/As(j /s)
7 Tn s Hc Hertz Hz s ' 1
II.3. Mt s n v khc hay s dng cn chuyn v h SIHin'nay, bn cnh h SI l n v chnh thc, trong ha
hc ngi ta cn dng mt s" n v khc khng thuc h S gi l n v phi SI. d dng trong qu trnh gii cc bi tp hai cng chng ti ghi li bng di y mt s" n v ngoi h thng cng cc h s' chuyn i v h SI.
N Tn ai lng vt l
n vi Khiu
Theo nh nghaTing Vit Ting Anh
1 Chiu i micromtnnomtAngstrm
micrometrenanometreAngstrom
n m n m
0
10'9m 10 m
2 Th tch lt litre I 10W3 Nhit tu bch
phnCelsius c T(K) =
(C)+273,154 Thi gian Pht,
giminutehour
minh
60s > 3600s
5 p sut tmtphebartormiiimt thy ngn
Atmospherebartorrmillimetre Hg
atmbarTorr
mmHg
1,13.10bPa 105Pa * 1atm
133 322Pa 133,322Pa
6 Nng lng ec calo ot gi electron- vn
ergCalorie Watt hour electron Volt
ergcal
w.heV
10*0-4.184J3600J
1,602.10"19J
7 in tch n v tnh in
Unitelectrostatical
ues CGS^ 10_19c
2,99798 Lc yn dyne dyn 10'SN9
m men lng cc
bai Debye D ^ 10_29C m2,9979
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III.4. Quan h gia th nguyn v mt s n v thng dng
N i lng Phngtrnh
Thnguyn
n v
xc nh SI CGS
1 Din tch s = / 2 L22m cm2
2 Th tch
coII> m3 cra3
3 Vn tc lV = ' t
LT*1 m s ' 1 cm s ' 1
4 Gia tc Va = t
LT' 2.9
m s cm s ' 2
5 Lc F = ma MLT' 2 kg m s g cm s~2
6 p sutF
p = - s
ML'lT"2 kg m 'V 2 -] -2 g cm s
7 Khi lng ring D = V
M* kg m ' 3 g cm ' 3
8 Cng (nng lng)
A = FZ ML2T*'2 kg m2 s' 2 g cm2 s ' 2
9 Cng sut N = t
m l 2t -3 1 2 *3 kg m s li -3g cm s
1 0 Tn s' 1 . - 2
f = T
T 1 -1s -1s
II.5. Cc bc bi, bc c so vi n v c s
Khi s dng h SI ngi ta thng ly cc bc gin c l
n v bc bi lOn hay n v bc c 1 0 "n vi n l s nguyn.
Bng di y ghi li cch dng ny.
Tip ng u
K hiu quc t
Bc c Tip ng u
K hiu quc t
Bc bi
Deei d 1 0 '1 Deca da 1 0 1
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Centi c 1 0 '2 Hecto h 1 0 2
Mili m 1 0 " 3 Kilo k 1 0 3
Micro n 1 0 6 Mega M 1 0 e
Nano n 1 0 9 Giga G 1 0 '1
Pico P 1 0 '12 Tera T 1 0 12
Fern to f 1 0 - 15 Peta P 1 0 15
Atto a 10-18 Exa E 1 0 18
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Chng I
MT S KHI NIM CHUNG
A. TM TT L THUYT
1. Theo Rutherford (1911) th nguyn t c cu thnh
bi ht nhn gm prton p, v ntron (n); lp v gm cc electron
quay quanh ht nhn.
Vy ngun t gm:
- Ht nhn vi s" proton l z, in tch q=l,6.10'19c v N
l ntron. Hai i lng ny c lin h vi nhau bng s' khi
A theo h thc A = N + z
- Lp v electron c in tch ng bng in tch proton
nhng ngc du v khi lng electron ch bng 1/1836 kh
lng proton, ngha l khi lng tp trung ht nhn.
2 . l vi nguyn t, ngi ta t dng n v kg m dng
n v khi lng nguyn t (u). n v ny c nh ngha nh
sau:
1 1 2 . 1 0 3 , _-!>/? ir r27iTT : : kg = 1 ,6 6 . 1 0 kg12 Na
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3. Mol l lng cht cha cng mt s phn t cu trc
nh 1 mol nguyn t H} 1 mol phn t H2, 1 mol ion H+... T
suy ra:
- S" phn t cu trc c trong 1 mol ca cht chnh hng
s" Avogaro: NA = 6,022.10
4. Quan h gia khi lng tng i (klt) v kh"! lng
tuyt i (KLT):
kt:KLT =
NaXc nh khi lng phn t theo t khi ca cht kh.
M a5. T khi d ca kh A vi kh B l d =
Mb
Ma, M b - khi lng phn t ca A, B.
Kh B l khng kh th d =_ Ma29 \
6 . Xc nh khi lng phn t theo th tch moi.
PV PnVn Cng thc Boyle Mariotte:
T T0
p, V, T - p sut, th tch, nhit iu kin th nghim.
P0, v 0, T0 - ng vi iu kin tiu chun: 760mmHg; 22,4; 273K
7. Phng trnh trng thi ca cht kh l tng
PV = nRT = RT M
n - s' mol kh; m- khi lng khi tnh bng gam (g); M - khi lng ca mt moi kh.
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hoc p = RT = RT VM M
d - khi lng ring ca kh.
8 . Nu c mt hn hp kh l tng nhit T c th tchV th p sut ton phn PT ca h c xc nh theo nh lutDalton
PT = X p, hayi
P T = ^ Z n .V
P; - p sut ring ca kh th i i - S^ mol kh i trong hn hp
B- BI TP C LI GII
1.1. Hy in cc s" liu cn thit nhng trng trong bng sau v:
K hiu nguyn t l57N 1880 19 T7, 9* - -S" khi 15 - - 23 -S" in tch ht nhn 7 - - 1 1 -S" p ro ton - - - 14 vS" electron 7 - - 14s
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1.2. 1) Trong mt th nghim in phn ngi ta thu c
27g nc. Hi: ,
a) C bao nhiu mol H20?
b) C bao nhiu nguyn t hiro?
2) Bit rng khi lng nguyn t tng i ca oxi l
15,99944. Tnh khi lng nguyn t tuyt i ca nguyn t ny.
Cho NA = 6,022.lO ^m or1.
BI GII
1) m = M.n suy ra n = = = l.mol H.;0M 18
Vy s phn t H20 l: 1,5.6,022.1023 = 9,0345.10~3 phn
t. Trong mt phn t HO th nguvn t H = 2 X s phn t
H30.
Vy s" nguyn t H l:
9,0345.1023.2 = 18,069.1023 nguyn t.
2) Khi lng nguyn t tuyt i ca oxi c tnh:
_____ 1 5 99944m(KLT) = - - 1 = 26,564.10 g.
6,022.1023
1.3. Trong nhiu php tnh ngi ta thng s dng hng s" kh R. Hy xc nh hng s cc h n v khe nhau.
a) Trong h n v SI.
b) Theo n v cal.K^.mol1.
c) Theo n v a tm i.K '1.moi'1.
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IBI GII
p dng phng trnh trng thi cho mt mol cht kh l
c) R = = 0,082 atm i.K^.m ol1273,15 \
1.4. Mt nguyn t X c bn knh l 1,44A, khi lng
ring thc tinh th l 19,36g/cm3. Nguyn t ny ch chim 74%
th tch ca tinh th, phn cn li l rng. Hy:
a) Xc nh khi lng ring trung bnh ca ton nguyn
t ri suy ra khi lng moi nguyn t.
b) Bit nguyn t X c 1 1 8 ntron v khi lng mol
nguyn t bng tng s* khi lng proton v ntron. Tnh s"
tng PV = RT. iu kin tiu chun
T0 = 273.15K; p0 = latm = 1,013.105 N /nr (Pa);
v 0 = 22,4/ = 2 2 ,4 . IC tV .
Theo n v SI: 1J - iN.m, vy:
R =
b) Do Ical = 4,184J nn gi tr R l:
R = i = 1,987 cal.K.m or4,184
proton.
B GII
a) Khi lng ring trung bin!
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y 7 4 J J - 100 ,'_100.19,36 _ . 3d = d => d = -d =----- 1 = 26;16g/cm100 74 74
Mt khc: m = v.d = 7cr3.d 3
m = .3,14(1,44.10*8)3.26,16 = 32,704.10'23g3
Vy khi lng ca ml nguyn t l:
M = N.m =. 6,022.1023.32,704.102: = 196,976g/raol
hay M ~ l97g/mol.
b) Theo u bi ta c th vit:
M = mp + mn = mp + 118 = 197
T biu thc ny ta suy ra s ht/proton cn tm: mp = 79.
1.5. 1) Trong s" cc ht nhn nguyn t ca nguyn t" th
ch (^?7Pb) c t s" N/Z l cc i v heli ( H e ) c N/Z l cc
tiu. Hy thit lp t s" N/Z cho cc nguyn t vi 2 < z< 82.
2) Mt nguyn t X c tng s" cc ht l 58, s" khi ca n
nh hdn 40. Hy xc nh s proton, s' electron v s ntron ca
nguyn t .
BI GII
Theo h thc A = z + N ta c th suy ra N = A - z. Vy:
1) T s' ca ch (l?7 Pb) l:zt
N _ 207-82 _ , co
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2 ) Nguyn t X c tng s' cc ht l 58 nn chc chn z nm trong gii hn 2 < z < 82.
Vy ta p dng t l phn 1 : 1 < < 1,524z z
Mt khc, ta li bit S = p + e + n = 2p + n=>n = S - 2 p
-HA - S - 2P s o ss r = -----suyra - 16,459 < p < 19,333 v 2p + n = 583,524 3
Da vo hai phng trnh ny ta lp bng bin lun:
p 17 18 19
n 24 2 2 2 0
A 41 40 39
Kt lun Loi Loi ng
1.6. Trong mt th nghim quang hp, kh oxi sinh ra, c
thu qua nc. Th tch kh thu c iu kin 22c v di p sut kh quyn 758mmHg l 186ml. Tnh khi lng oxi bit
rng p sut hi nc 22c l 19,8mmHg.
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BI GII
Trc ht hy tnh p sut ring ca oxi. V p sut chung
bng tng p sut ring ca tng cht, nn
p0a =PT- P H , 0 = 758 - 19,8 = 738,2 mmHg = 0,971 atm
Khl ng oxi c tnh t phng trnh trng thi ca
kh l tng:
PV = RT M
___PVM _ 0,971.0,186.32m = = - = 0,239g.
RT 0,082.(273 + 22)
1.7. 7 kg oxi c cha trong mt bnh cu di p sut 35 atm. Sau mt thi gian s dng;, p sut o c l 12atm. Hi c bao nhiu kilgam oxi thot ra.
BI GII
H qu ca nh lut Boyle-Mariotte cho ta mi quan h gia t trng ca kh v p sut:
dL=pL d2 p2
rii.v P d2.v p3
y V l th tch ca bnh cu.
V d. V = m ; m l khi ng kh; nn
M = j j
m 2 P2
Thay mx = 7kg; P = 35atm; p.; = 1 2 atm vo phng trnh trn ta c
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_ _ IX11P2 _7.12_ 0 1112 = p T = 1 5 24k
Vy lng oxi thot ra trong qu trnh s dng bng: 7 - 2,4 = 4,6 kg.
1.8. Mt bnh dung teh 247,2 cm3, c khi lng 25,201 g cha khng kh. Mt lng benzen c a vo bnh ri un nng ti 100C. Benzen bay hi ko theo ton b khng kh ra khi bnh. Ngi ta bnh ngui tr' li nhit phng, trong trng thi m ri cn. Khi lng lc ny l 25,817g. p sut kh-quyn l 742mmHg. Tnh khi lng mol ca benzen v vit cng thc phn t benzen bit rng cht ny ch gm hai nguyn t' cacbon v hiro.
BI GII
T cc gi tr ca p, V v T c th tm c s mol be zen v t khi lng ca bnh trc v sau khi cha hi benzen c th tm c khi lng m ca benzen.
V = 247,2cm3 hay 0,2472/
T = 273 + 100 = 373K
p = 742mmHg hay 742/760 .= 0,976atm
S" moi n ca ben2 en:
n = PV/RT = 0,976.0,2472/0,082.373 = 7,88.10'3mol
Khi lng be zen = (khl lng bnh + khi lng khng kh + khi lng hi ngng t) - (khi lng bnh + khi lng
khng kh)
- =25',817 - 25,201 = 0,616g
Khi lng mol M = = 0,616/7,88.10'3 = 78,2 g/mol1
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Cng thc ca bezen (CH)X : X = xt 612
Vy benzen c cng thc C6H6
c-BI TP T GII
1.9. 1) Tnh khi lng mol nguyn t ca Mg; p nu bit khi lng tuyt i (KLT) ca chng l: mMt = 40,358.x.0"27kg; mp = 51,417.10'-7kg.
2) Xc nh-khi lng tuyt i ca N v AI nu bit khi lng tng i (klt) ca chng l: MN = 14,007u; MA1 = 26,982u.
p s: 1 ) MMg = 24,307 g/mol.
Mp = 30,986 g/mol.
2) mN = 23,255.10"24g.
~~~~~ mA1 = 44,798.10'24g.
1.10. Nguyn t bc (Ag) c khi lng moi nguyn t v khi lng ring trung bnh ln lt bng 107,87 g/mol v10,5 g/cm:i. Bit nguyn t ny ch chim 74% th tch ca tinh th. Hy xc nh bn knh nguyn t ca bc (Ag) theo A.
p s: rAg = 1,444A.
1.11. i vi nguyn t km (Zn) ngi ta bit bn knh nguyn t v khi lng mol nguyn t ln lt c cc gi tr l 1,38A; 65g/mol.
a) Xc nh khi ng ring trung bnh ca Zn (g/cm8)
b) Bit Zn khng phi l khi c m c khong rng nn trong thc t n ch chim 72,5% th tch ca tinh th. Hy cho bit khi lng ring thc ca Zn l bao nhiu?
p S: a) 9,81 g/cm3; b) 7,11 g/cm3
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1.12. Kim loi M tc dng va vi 4,032 kh CL iu kin tiu chun thu c 16,02 g MC13 theo phng trnh:
2M + 3C12 = 2 MC3
a) Xc nh khi lng nguyn t ca kim loi M.
b) Tnh khi lng ring ca M; suy ra t l phn trm ca th tch thc vi th tch ca tinh th. Bit M c bn knh r = 1,43A; khi lng ring thc l: 2,7 g/cm3
- p s: a) M = 27b) d = 3,66 g/cm3; %: 73%
1.13. Mt cch gn ng gia bn knh ht nhn rn v s" khi A ca mt nguyn t c h thc: r n = 1,8.10"1;\ A!/:icm. Hy xc nh khi lng ring d(g/cm3) ca ht nhn nguyn t.
p s: = 6,80.1013 g/cm3
1.14. Da vo nh ngha hy xc nh khi lng nguyn t ra kg cho mt n V khi lng nguyn t (lu). T kt qu tnh c, hy suy ra khi ng nguyn t tuyt i ca oxi, bit oxi c khi lng nguyn t l 15,9974 u.
p s': lu = l , 6 6 .1 0 27kg; moxi = 26,567.10"24g1.15. Mt nguyn t X c tng s" cc loi ht l 193,
trong s" proton l 56.
a) Hy xc nh s" khi ca X
b) Tnh khi lng nguyn t v khi lng ht nhn ca nguyn t X va tm c. Cho bit t s" khi lng ny t nu nhn xt cn thit. Cc gi tr khi lng ca p, n, e xem bng ph lc (cui sch).
p s": a) Ax = 137 b) m = 229,3579.0 '2^ kg mh/nhn = 229,3070.10'"7kg
_E n/t_= 1 , 0 0 0 2 2^h /nhn
Khi lng nguyn t hu nh tp trung ht nhn
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1.16. Hon thnh s liu ghi trong bng di y
Nguyn t A z N N/ZCa 40 2 0I 127 74
TI 204 1,52Pb 82 125Np 237 73Pb - 208 1,53
1.17. Mt qu bng c n hi cao, c th tch ban u1 ,2 lt 1 atm v 300K. Qu bng ny bay ln tng bnh lu c nhit v p sut tng ng bng 250K v 3.1CT3 atm. Tnh th tch ca qu bng trn tng bnh lu. Chp nhn kh l l tng.
p s": 3,3.10^ lt.1.18. Kh than t (CO + H;) c to ra khi t c vi hi
nc theo phng trnh phn ng: c + HoO = c o + H2. Khi t chy mt tn than cc trng hi nc c 1 0 0 0 c th to ra c mt th tch kh than t l bao nhu? Ti 2-0C di p sut lOOatm.
p s": 4,02.10104 lt1.19. Mt bnh dung tch 2 cha 3g C 02 v 0 ,1 0 g H2
17c. Tnh p sut ring ca tng kh v p sut ton phn cc kh tc dng vo thnh bnh (gi thit kh l l tng).
p s": PC0 2 = 0,812 atm; PH = 0,3; p = 1 ,1 1 -atm
1.20. i vi lmol kh N9 0c s ph thuc ca th tch vo p sut c cho di y:______________________
p/atm 1 3 5 v/cm a 22405 7461,4 4473,1
Xc nh hng s' kh R bng:a) Tnh tonb) th (V th PV/nT ph thuc v p ri ngoi suy
ti p = 0 )L21. Mt bong bng kh bn knh l,5cm y h c nhit
8,4c v c p sut 2 ,8 atm, ni ln mt nc p sut kh quyn latm, nhit 25c. Hi kh ti b mt ca h nc th bn knh bong bng l bao nhiu (th tch hnh cu bn knh R l 4/3ttR3)
p s": 2,2 cm.
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Chong II
NGUYN L I CA NHIT NG Lc HC. NHIT HO HC
A- TM TT L THUYT
1, Ni dung ca nguyn l I
Mt h nhit ng khi trao i nng lng vi mi trng
xung quanh di dng nhit Q v cng A th tng i s" Q + A
lun lun l mt hng - S ch ph thuc vo trng thi u vcui ca h, hon ton khng ph thuc vo ng i:
\ 2 ' -(Trng thi u) 1 (Trng thi cui)
Q(l) + Al) = Q
-
Trong 3 i lng nhit ng , A, Q ch c i lng u l hm trng thi; 2 i lng cn li l nhng i ng c trng
cho qu trnh, tc l chng ph thuc vo ng i.
Quy c v du ca nhit v cng:
- Nhit Q v cng A c tnh l dng (Q > 0; A > 0) nu
h nhn nhit v nhn cng t bn'ngoi.
- Nhit Q v cng A c tnh l m (Q < 0 ; A < 0 ) nu h
nhng nhit v sinh cng cho bn ngoi.
T biu thc (1) ta thy rng i vi h c lp (khng trao
i g vi bn ngoi) Q = 0, A = 0, do AU = 0. Vy trong h c
lp ni nng c bo ton.
2. Cc biu thc v cng v nh >ng mt s qu trnh
- Cng do h thc hin cho b ngoi c xc nh bng phng trnh:
Vi Pc l p sut ngoi, 'dv l bin thin th tch. i vi
nhng bin i v cng chm, c th xem Pe = p vi p l p sut
ca h do cng dn n th tch s l:
a) Cng
SA = -pe. V
1
- Qu trnh ng tch dV = 0. Suy ra; Ay = 0
- Qu trnh ng p p = const
a ; = -P(V, - v o = -P.AV
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I vi h ng th ca kh l tng, s bin thin th tch
2 trng thi 1 v 2 l do s bin thin s" mol 2 trng thi ,
nn
Ap = -AnRT (3)
Qu trnh ng nhit (T =const) i vi 1 mol kh l tng:
'> _2rdV v.>At = - P.dV = ~RT [ = -RTln
J J V v 71 1 1
T = const th tch ca kh l tng t l vi p sut, do :
At = - R T ln - = -R T ln-!- (4)^ V, p,
b) Nhit v nhit dung
Nhit dung c c xc nh nh sau:5Q = Q dt dT
QTrong iu kin ang tch ta c: Cy =
T
v trong iu kin dng p ta c: c =SQp
p CT
Trorig h SI, n v nhit ung l Jun/.
Vn dng nguyn l I cho kh l tng ta c:
d = Q + 5A = Q - P.dV.
Vi iu kin ng tch dV =. 0; d = Qv - Cv.T.
l vi 1 mol kh l tng:.. 67
A \
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Qv = AU = Jc vT = CV2-T ,)1
nu Cv khng i trong khng nhit t n T2.
Vi iu kin ng p:
d + PV = Q hay d(U + PV) = 5QP;
+ PV = H. H l Entanpi;
Vy: dH = 5QP = C.dT hay AH = Qp = jc pdT1
i vi mt mol kh l tng v Cp khng ph thuc nhit
th: AH = Qp = Cp (T2 - Ti).
Vi iu kin ng nhit T = const.
Ni nng u v entanpi H ca kh tng ch ph thuc nhit , khng ph thuc vo th tch cng nh p sut, do :
a u t a h t 0 .
- Quan h gia Qt) v Qv ca phn ng ho hc din ra trong pha kh:
Qp = Qv + AnRT (5)
Vi An l hiu gia s" mol kh v phi phng trnh phn
ng v s mol kh v tri ca phng trnh phn ng.
3. Nhit ca phn ng ha hc
T nh lut Hess v nhit ca phn ng ho hc c th
rt ra mt h qu ca s tnh nhit ca phn ng da vo nhit
hnh thnh v nhit t chy nh sau:
>
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IAHPU = E(AHht) cui - I(AHkt) u (6 )
AHp = Z(AHe) u - L(AHdc) cui (7)
Nhit ca phn ng xc nh theo (6 ) v (7) l nhit nhit
khng i.
Khi nhit thay i th nhit ca phn ng cng thay oi theo. S ph thuc ny c biu th bng nh lut Kirchhoff
nh sau:
( ^ ) = A C P= 2 Cpcul- C pcr&
Sau khi ly tch phn ta c:
T
AHT -AHT] = jACpdT=ACp(T2 ) (8 )
T,
Vi ACp l hng s" trong khong T h> T2 .
T nhit ca phn ng ha hc c th tnh c nng lng
lin kt ca cc cht c mt trong phn ng.
AH = z nng lng lin kt cc cht u - nng lnglin kt cc sn phm (9).
Nng lng in kt y c nh ngha l nng lng
cn thit ph v lin kt ha hc to ra cc nguyn t t o
th kh.
B- BI TP C LI GII
y II .l . Gin n ng nhit 0,850 moi kh l tng t p sut
15 atm v nhit 300K ti p sut latm. Tnh cng gin n:
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a) Trong chn khng;
b) Khi p sut ngoi khng i l 1 atm;
c) Khi qu trnh l thun nghch.
BI GII
a) V l chn khng nn P = 0 do A = -PC.AV = 0.
b) A = -P p(V2 -V 1).
-
2 ~~ p 7 _ ( 1 o2 _>. v9 - v x = nRT ------
V = 5 1 l p 2 p j ?
1 p, , ^ '
A = -n R T E ,(^ --^ -)2 1 , -
. 1 i r - - k - 0 , 8 5 0 ( ^ 3 0 0 . ! ^ - ^ ) ~ /Q g o
. ^
A = -19,5 a tm i hay A = -19,5. 101,34J = -1980J.
c) A = -PdV = dV = riRTdlnVy
A = -nRTn ^ = - is p T ln ^
= -0,850,8,314.300-ln 1
Vy A = -5740J.
IL2. Tnh Q, A, A trong qu trnh nn ng nhit, thun
nghch 3 mol kh He t 1 atm n atm 400K.
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BI GII
Mt cch gn ng c th xem He l kh l tng, do
AUt = 0. T nguyn l I suy ra
5- Q = -A = nRTln = 3.8,314.400.1n - = 1,61.104J
P1 1
Vy: A = 1,61.104J; Q = -1,61.104J :
S nn ng nhit 3 mol He l mt qu trnh ta nhit.
II.3. So snh s khc nhau gia AH v A i vi cc bin
i vt l sau y:
a) 1 mol nc 1 mol ncc 273K v latm.
b) 1 mol nc -> 1 mol hi nc 373K v latm. Cho\bit 273K, th tch mol ca nc v nc lng bng 0,0196 \l/mol v 0,0180 1/mol v 373K th tch mol ca nc lng v
hi nc tng ng bng 0,0188 1/mol v 30,611/mol.
BI GII
Trong c hai trng hp qu trnh l ng p nn:
AH = AU + A(PV)
= A + P.AV AH - AU = P. AV
a) AV =V L-V R
= 0,0180-0,0196
= -0,16.10'2l/mol
AH - AU = p. AV = 1.(-0,16.102) = -Q,l6 .icr2 .atm
hoc: AH - A = - 0,16 J/mol
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b) AV = VH - VL = 30,61 - 0,0188 = 30,59 1/mol
AH - A = P.AV = 1. 30,59 l.atm hoc 3100 J/mol
So snh (AH - A) (a) v (b) cho thy s khc bit gia
AH v A l qu nh, c th b qua i vi cc pha ngng kt,
song s khc bit gia hai i lng ny l rrg k nu l pha
kh. T (a) thy rng AU > AH do s gim th tch khi nc
nng chy, kt qu ca vic h nhn cng t bn ngoi.
X II.4. t chy mt mol Benzen lng 25JC, latm to ra
kh C 0 2 v nc (H20) (Z), ta ra mt nhit lng bng 3267kJ.
Xc nh nhit hnh thnh ca Benzen lng iu kin cho v
nhit v p sut, bit rng nhit hnh thnh chun ca co*,
H20 (Z) tng ng bng - 393,5 v -235,8 kJ/mol.
BI GII
S t chy mt mol benzen theo phng trnh phn ng
C6H6 + 1 - 0 2(k) = 6 CO(k) + 3H20 (1).
Gii phng ra mt nhit lng A Hp = -32,67kJ/mol\
p dng phng trnh (6 ) ta c:
AHp = 6AHtC0% + AH^tH2Q - AH^tCgH6 - 7 AH^t0i? r 3267 =
= ( - 6 X 3 9 3 , 5 ) + ( - 3 X 2 8 5 , 8 ) - AH(hlC;H( - 0
Vy AHjJtc H = 49kJ / mol
II.5. Trn 50ml dung dch HC1 0,20M vi dung ch NaOH
0,20M trong mt nhit lng k, nhit tng t 22,2c ln
23,5c.
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Xc nh nhit trung ha (tnh ra kJ/mo) theo phn ng:
H30 + + OH' = 2H20.
Cho bit t trng ca hn hp dung dch long l Ig/m v
nhit dung ring ca nc l 4,18J/g.K
BI GII
Th tch ca hn hp khi pha trn bng 50 + 50 = 100ml, do c khi lng bng l.OOg. Bin thin nhit gn lin vi
phn ng trung ha l: 23,5 - 22,2 = l,3c = 1,3K.
Lng nhit Q = m.e.At = 100 X 4,18 X 1,3 = 540J-
S' mol HC c trong 50ml dung dch 0,20M.
^00 ,2 0 .-- = 0 , 0 1 moi.
1000
Tng t s moi NaOH bng 0,01 moi.
Vy 0.01 moi H;30 + .phn ng vi 0,01 moi 0H gii phng
ra 540J. Nhit trung ha ng vi 1 moi s l: 54000J hay
54kJ/mol
Vy vi phn ng: HC + NaOH = NaCl + KgO. AH = -
54 KJ/moI-
I.6 . I vi phn ng: N, + 0 9 = NO 25c v latm.
AH = 90,37 kJ. Xc nh nhit ca phn ng 558K, bit rng
nhit dung ng p vi lmol ca N2, 0 2, NO ln lt bng
29,12; 29,36 v 29,86 J/K.mol.
BI GII
p dng nh lut Kirchhoff ta c:
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t 2
AH = AH^ + jACpdT
558
A H 558 = A H 298 + j A C p d T
298
V Cp ca cc cht khng ph thuc T nn:
AH58 = AH98 + ACp(558 - 298)
= 90,37 + (29,86 - . 29,12 - 29,36).icr3.(558 - 298)
AH? 58 = 90,53kJ
Ch :
- Trng hp Cp l mt hm ca T v ni chung s ph
thuc c dng Cp = a + bT + CT2 +...hoc Cp = a + bT + CT 2 thi
khi tnh, ACp khng c a ra ngoi du tch phn v c dng,
chng hn ACp = Aa + AbT + ACT2 + ...
II.7. Xc nh nng lng lin kt trung bnh ca mt lin
kt C-H trong metan bit nhit hnh thnh chun AHjCH = -
74,8kJ/mol; nhit thng hoa ca than ch bng 716,7 kJ/mo v
nng lng phn ly phn t H2 bng 436 kJ/mol.
BI GII
Nng lng lin kt trng bnh ca mt lin kt C-H trong phn t CH4 bng 1/4 nng lng. Theo nh ngha, nng lng
lin kt trong CH4 l AH(298 ca qu trinh:
CH4(k) C(k) + 4H(k).
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Vn dng nh lut Hess, AHoy* ca qu trnh phn ly
phn t thnh cc nguyn t t do th kh c xc nh nh chu trnh sau:
Vi l nhit thng hoa ca C; AHpL l nang lng
phn ly phn t.
Vy:
A^ 2 9 8 ~ _ A ^ht.CH 4 + +2AHpL
= -(-74,8) + 716 + 2x436
~ 1663,5 kJ/mol
Phn t CH4 c 4 Hn kt C-H; do nng lng 1 lin kt
C-H bng = 4i6kJ/mol
Bi ton trn cp ti vic tnh nng lng in kt khi bit nhit hnh thnh. Ngc li, bit nng lng lin kt c th tnh c nhit ca phn ng, chng hn i vi phn ng:
AH&U = z nng lng lin k a C9 v HI - nng
lng lin kt ca I2 v HC1.
c r ' ' C(k)- + 4H(k)
Cgr + 2H2(k)
4
Ch :
Cl2 + 2 HI (k) = I2(k) + 2HC1 (k)
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Nng lng lin kt ca Cl2> HI, I2 v HC1 tng ng bng
239, 297, 149 v 431 kJ/mo.
AHp = 239 + 2.297 - 149 - 2.431 = -178kJ
L 8 ^)l mol nc nng chy 0 c, 1 atm, hp th mt
nhit ng bng 6019,2J. Th tch mol ca nc v ca nc
lng bng 0,0196 v 0,0180 lt. Tnh AH v A i vi qu trnh
ny.
BI GII
V Qp = a h nn AH = 6019,2J
tnh A ta vn dng cng thc AH = A + A(P.V).
;i vi qu trnh ng p
A(P.V) = P.AV = P(V2 -Vj) =
=1(0,0180 - 0,0196) =
= -1,6.10' 3 atm.l = -0,1630J
A = AH - P.AV = 6019,2 - (-1,63.10-2) = 6019.2J
II.9. 25c v latm s hnh thnh 1 mol c o t graphit v oxi c AH = - 1I0,418J: Xc nh AU nu lmol graphit c th tch
bng 0,0053 lt.
BI GII
T phn ng hnh thnh CO:
Cgr+I0* 00
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1S bin thin s moi kh l An = - = 2 2
Mt khc bin thin th tch ca h (AV) do s hnh thnh
kh l AV = 1/2. 24,4/ = 12,2Z, n hn rt nhiu so vi s gim
th tkh ca grapht do c th b qua th tch graphit.
. AH = A + AnRT
-110,418 = A + .8,314.298 2
AU = -1349, 2J
11.10. Tnh nng lng Hn kt O-H trong phn t nc
bit cc d kin:
K20 (Z) = H20 (k) AH = 40,6 kJ/mol (1)
2H (k) = H2 (k) AH = -435 kJ/mol (2)
0 2 (k) = 20 (k) AH =-489,6 kJ/mol (3)
2H2 (k) + 0 2 (k) = 2H2 (G) ) AH = -571,6 kJ/mol (4)
/B i g i i s\
Nng lng lin kt l Ting'lng trung bnh cn ph
v mt lin kt xc nh trong phn t v to ra cc nguyn t
hay cc gc. Phn t H2 c 2 lin kt o - H. Nng lng trang
bnh ca mt lin kt 0 - H s bng 1/2 hiu ng nhit ca phn
ng H20(k) = 2 H(k) + 0(k).
tnh hiu ng nhit ny ta vn dng nh lut Hess.
Ly phng trnh (4) nhn vi 1 /2 ri cng vo cc phng
trnh (1) v (2 ) ta c:
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(-571,6. - ) + 40,6 + (-435) = -680,2 kJ 2
Ly phng trnh (3) nhn vi 1 /2 ri tr i tng'trn (-680,2):
(489,6. - ) - (-680,2) = 925 kJ 2
Vy hiu ng nhit ca phn ng-
H20 (k) = 2H (k) + o (k)
l 925 kJ suy ra nng lng to ra 2 lin kt 0 - H l -925 KJ,v
nng lng trung bnh ca 1 lin kt o - H l -925/2 = 462,5
kJ/mol
Ch : cc tnh ton trn u da vo s chuyn ha
c thit lp trn c s nh lut Hess:
H2(k) + | o 2(k) A l4) > H20 (l)
AH(1). 2
AH(3)
y
-AH(:
2H(k) + 0(k) H, ->H20 (k)
1 1 .1 1 . Tnh Hft|3 i vi phn ng c o + (>2 = CO bit
298K nhit hnh thnh chun ca c o v C02 l -110,5 v -
393,5 kJ/mol ;
Cp (C) = 26,53 + 7,7.10":iT J/K.moi
Cp (C02) = 26,78 + 42,26.10':iT J/K.mol
c p (02) = 25,52 + 13,60.10'3T J/K.mol
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BI GII
AH9 8 (P.U) = AH298 ht(C02) - AH298.ht(CO)
= -393,5 - (-110,5) = -283 kj
Da vo nh lut Kirchhoff tnh AH 73 (P.U):
473
AH?73 = AH98+ ACpdT298
vi
ACp = Cp(C02) - [CCO) + c p 0 2] = -12,51 + 27,76.10'3T
473
Cui cng AH73 = -283000 + [(-12,51 + 27,76. lO3 T)dT298
= -283000 - 12,51(473 - 298) + 27,7610 3 (4732 - 2982)
- 283000 - 2190 + 1870
= -283320 J/mol
AH7 3 (P.) = -283,320 kJ/mol.
C- BI TP T GII
11.12. Xc nh cng dng nng mt vt khi lng 30
kg ln mt cao 2 m.p s: 588J.
11.13. Tnh cng thc hin bi phn ng gia km v axit sunfuric long khi thu c mt mol kh hydro iu kin 0 c v 1 atm.
p s: -2.27 kJ
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11.14. Tnh AU v AH trong qu trnh un nng 55,4g Xe t 300 n 400K, bit rng i vi 1 mol kh Xe Cv= l2.47J/K.mol
p s: AU = 526J; AH = 877J
II. 15. Nhit dung ng p ca lmol ng dc cho bi
phng trnh Cp = 22,65 + 6,3.10: TJ/K.
Tnh AH khi t nng lmol ng t 300 n 400K
p s: AH == 24S5J.
11.16. Tnh nhit ca phn ng quy v kg nhm i vi
phn ng: 2AI + FesOfl = 2Fe + AI9O3.
Cho bit AI = 27; AHj[tA o = -1667-,82 kJ/mo v
^ h tP e o = -819,28 kJ/mol.
p s: 15712,6 kJ
11.17. Tnh nhit hnh thnh ca tan bit:
Cp. + 0 2 = CO2, AH = -393,5 kJ
H2 + 0 , = H20 (0 AH = -285,8kJ.2r
2C2H6 + 7 0 , = 4C 0, + 6HS0 ); AH = -3119,6kJ
p s': -84,6 kJ
11.18. Chic bt la gas cha butan lng (AHJtbutan =
127kJ/mol). Xc nh lng nhit ta ra khi Ig btan lng trong
bt la b t chy; gi thit rng sn phm ca s t chy l
C02 v hdi H20.
p s: -4.7kJ
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% IL19. Nhit hnh thnh trong dung dch nc 2C ca
HFaq; OHaq; Faq, ln lt bng -320,lkJ/mol; -229,94 kJ/mol v -
329,1 lkJ/mol . Nhit hnh thnh 25c ca H20 lng bng - 285,84kJ/mol.
a) Tnh nhit trung ha ca HFaq theo phn ng:
H V + D H ^ - J - j+ H jO (1 )
b) Tnh nhit in ly ca HF trong dung dch
HFac=H:q +OH-q
Bit nhit trung ha ng vi phng trnh:
K q + 0H q = H2G 0) '55,83 kJ/mol.
p sp': a)-64,91; b) -9,08.
11.20. Tnh aH ^ 98 i vi cc phn ng sau:
a) 2H2S (k) + 302 = 2HaO () + 2S02.
. b) 2H2S (k) + 302 = 2H20 (k) + 2S02.
c) 2HNS (k) + 2 NO = H20 2 (l) + 4N2.
Bit nhit hnh thnh ca H2S, HoO(0, H20(k), S02. KNo,
NO v H5O2 ln lt bng -20,63; -285,83; -241,81; -298,83;
294,1; 90,25; -187,78 kJ/mol.
Cng i vi cc phn ng trn, tnh AH^, K bit:
Cht H2S . 0 2 H20 () H20 (k)1
S02
Cp [J/molK] 34,23 29,35 75,29 33,57 39.87
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Cht h n 3 NO h 20 2 n 2
rp[J/mol.K] 4 3 , 6 8 29,84 89,1 29,12
p s: -1124,03; -1036; -956,5 kJ/mol; -1118,7; -1036,7.
IL21. vi phn ng: 2 C9 + Oo = 2C09; Nhit ung
ng p ca cc chttrong khong t 298 n 2000K c dng
chung Cp = a + bT + cT'2. Cc h s a,b,c ca cc cht c cho
di y:
Cht
0 2
CO
co*
a[cal/.molJ
7,16
6,79
10,55
b.1 0 3
1
0,89
2,61
-5C . 1 0
-0,40
-0,11
-2,04
Tnh AH^ooo
Bit AH,98 ca phn ng'bng -565,96kJ
p s: -564,41kJ
^ 11.22. Tnh nng lng lin kt trong phn t PC13, t
xc nh nng lng lin kt trng bnh ca mt lin kt p - C.
Cho bit:
- Nng lng lin kt c Cl = 239 kJ/mol.
- Nng lng thng hoa ca p = 316,2 kJ/mol
- Nhit hnh thnh ca PCI3 (k) = -287 kJ/mol
p s: 961,7 kJ/mol; 320,56.kJ/mol
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11-23. Xc nh nhit t chy chun AHgg ca metan:
CH4 + 20 2 = C02 + 2H20 (k).
Bit nng lng lin kt trung bnh ca:
c - H bng 414 kJ/mol
0 = 0 498,8
c = o 724
0 - H 460
p s: -034,4 kJ
11.24. Mt kh l tng no c nhit dung mol ng tch
mi nhit Cv = 2,5R (R l hng s" kh).
Tnh Q; A; AU v AH khi lmol kh ny thc hin cc qu
trnh sau y:
a) Gin n thun nghch ng p t (latm; 20dm3) n
(1 atm; 40dm3).
b) Bin i thun nghch ng tch t trng thi (latm;
40m3) n (0,5atm; 40dm:).
c) Nn thun nghch ng nhit t (0,5 atm; 40n3) n
(latm; 2 0 dm3).
Hy phc ho mi qu trnh trn cng mt gin P-V, ri
tnh Q; A; A v H cho chu trnh ny.
' 11.25. Xc nh nhit hnh thnh Imol AlG da vo cc
phng-trnh nhit ha hc di y:
p s: a) Q = 7,09 kJ; A = 5,06kJ
b) A = 0; Q = -5,07 kJ; AU = -5,07; AH = 7,S.
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Al20 3(r)+3 C0 Cl2(k)=3 C0 2(k)+2 AlC1.3(r) A! =-232,24kJ
CO(k) + Cl2(k) = COCl2(k) AH2 =-112,40kJ
2Al(r) + - 0 2(k) = Al20 3(r) AH3=-1668,20kJ2
bit rng nhit hnh thnh ca c o v co? tng ng bng
-110,40 v -393,13 kJ/mol.
p s: -694,71 kJ
11.26. Tnh lng nhit ta ra 25c trong s hnh thnh
32g Fe20 3 t cc nguyn t" iu kin ng tch, bit rng trong
s hnh thnh FeO AH = -268,77 kJ v s oxi ha FeO thnh
Fe20 3 ta ra 2027,30J, vi lg FeO iu kin ng p;
nbng nhit lng ny u c xc nh 25c.
p s: 165,15 kJ
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Giing III
N6UYN L II CA NHIT NG LC HC
A- TM TT L THUYT
1. Entrpi v s tnh Enprpi trong mt s q u trnh
Nguyn l II thit lp c rng i vi qu trnh thun
nghch nhit ng t s" gia lng nhit v cng nh v nhit
tuyt i l mt vi phn ton phn ng ca mt hm s no ,
hm Entropi S:
V Entrpi l mt hm trng thi nn i vi qu trnh
thun nghch i t trng thi 1 n trng thi 2 , bin thin
Entrpi AS s bng:
(1)
2SQ
(2)
Nu qu trnh thun nghch l ng nhit (2) tr thnh:
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Nu qu trnh thun nghch l on nhit (Q = .0) th dS = 0;
AS = 0. vi qu trnh khng thun nghch nhit ng th:
> (-^ t ) k t n _
Nu qu trnh khng thun nghch l ng nhit th:
> k t n
Nu qu trnh khng thun nghch l on nhit Q = 0 th
. dS > 0, AS > 0 (6 )
Mt cch tng qut biu thc ton ca nguyn l II l:
dS > ^ (7)T
Khi h nhit ng c gp vi mi trng xung quanh m thnh mt h c lp th:
c lp (A ^ h nhit ng ^ m i trng ) ^ ( 8 )
Nu trong h c lp ch din ra qu trnh thun nghch th:
SHcip = 0 s = const
Nu trong h c lp ch din ra trong qu trnh khng
thun nghch th ASHccip > 0 (S > St).
V ngha vt l, entrpi s c trng cho tnh hn lon ca h nhit ng.
AS trong mt s' qu trnh:
p = const
T
ASp = J^p
-
Vi Cp l hng s:
ASp = CoinT,
V = const:
ASV = Cvln Tj
(Cv l hng s' trong khong Tj, T2).
AS ca kh l tng:
i vi 1 mol kh l tng
AS = R ln ^ - + Cvln-Jjf (Cv = const)V1 I
hocp _ T
AS = -R In + Cp 111 (Cp = const) (12)
2. Th nhit dng G v F
T nguyn l II vi s xut hin hm entrpi s, ta bit rng trong h c lp ch nhng qu trnh no lm tng entrpi
(AS > 0) mi c th t xy ra.
vi nhng qu trnh xy ra khng trong iu kin c
lp, th c nhng hm s" khc vi nhng bin s" tng ng;
l nhng hm s" G v F vi cc bin s tng' ng l p, T v V, T. Cc hm s" G v F ny l cc th nhit ng v c nh ngha nh sau:
G = H - TS, 'F = u - TS.
Th nhit ng G cn c gi l nng lng t o Gibbs
(Gip-X): F cn c gi l nng lng t do Helmholtz (Hem Hon X). G v F u c gi l nng lng t do v l phn nng lng t o chuyn thnh cng.
(10)
(11)
(9)
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T cc biu thc nh ngha i vi G v F ta c:
i vi G T, p = const; G = H - TS
hay vi qu trnh hu hn
AG = AH - TAS (13)
i vi F T, V = const; dF = d - TdS
hay i vi qu trnh hu hn
AF = A - TAS (14)
Cc hm G v F c dng lm tiu chun nh gi chiu hng ca qu trnh. Thc vy nu qu trnh t xy ra
T.P=const thi phi km theo s gim ca G tc l aG =G2-G1< 0.
Cn T,v = const qu trnh din bin theo chiu gim ca F tc l AF = F - Fi < 0.
vi phn ng ha hc, kh nng tham gia vo phn ng ca cc cht c c trng bng mt khi nim i lc ha
hc. o i c ha hc AG hoc AF tu theo iu kin din bin ca phn ng ng nhit, ng p hay ng nhit ng tch.
i vi phn ng ha hc din ra iu kin chun th:
y, AG^t . bin thin nng lng t do chun ca s
hnh thnh hp cht t cc n cht. i vi n cht AGJ{, =0 .
B - BI TP C LI GII
IIL l. Tnh AS trong qu trnh gin n ng nhit 2mol kh
l tng t 1.51 n 2,4L
AG=XA9ht.snphm (15)
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BI GII
p dng phng trnh (1 1 ) trong iu kin T = const, i
vi 2 mol kh:
AS =.2. 8,314 X in ^ 4 = 7,8 J/K 1 ,0
IIL2. Tnh AS - trong qu trnh un nng 200 gam nc
t 10c n 20c p = const, bit Cp ca nc bng 75,3J/K.mo.
BI G
Ap dng cng thc
AS = nCpln -
1Ta c
AS = . 75,31n = 29J/K 18 283
( n i Tnh AS ca qu trnh khuch tn vo nhau ca
lmol kh N2 v lmol kh 0 2. trng thi nguyn cht mi cht
kh cng mt iu kin v nhit , p sut v th tch.
BI GII
S khuch tn ca hai kh lm tng gp 2 ln th tch
T = const do :
AS0 2 = R ln ^ - = Kln2 = 2,303Rlg2
= #2,303Rlg2
AS = AS0 + ASNs^2,303Rlg2 = 11,5J/K
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IXL4. Tnh AS ca phn ng 4Fe + 30 = 2Fe90,3- Bit s ca Fe, 0 2 v Fe20 3 tng ng bng 27,3; 205 v 87,4 J/Kmol.
BI GII
T phng trnh (12) Ta c:
ASp = 2Spe2Q3 ~4Spe - 3 Sq 2
= (2. 87,4) - (4. 27,3) - (3.205) = -549,4 J/K.
II.5. Hy tin on du ca AS trong phn ng sau:
a) CaCOs = CaO + C02.
b) NH3 + H C l(k)-N H 4Cl(r)
c) BaO(r) + C02(k) = BaC03(r)
BIGI
a) AS > 0; b) AS < 0; c) AS < 0.
III.6 . Tnh AG9S trong s hnh thnh lmol nc lng bit
cc gi tr Entrpi chun ca H2 v 0 2 v H9O ln lt bng:
130,684; 205,133; v 69,91 J/K,moi v AH ca s hnh thnh
nc lng bng -285,83kJ/mo.
BI GII
AG = AH - TAS.a q 0 q O q O 1 gOAfc> ~ tH20 " aH2 2 2
= 69,901 - 130,684 - . = -163,34J/Kmo.2
AG!w = -285830 - 298.(-163,34) = -237,154kJ
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1I7. Tnh AS? 98 , AHS98v AG98 i vi phn ng
phn huy nhit CaCO.3, bit:
CaCOs CaO C 02
S?9S /J . K_1.m o rl ... +92,9 . . .38,1 213,7
A H ^./kJ.m or1... - 1206,90 -635,10 -393,50
BI GII
CaCOs = CaO + C 02.
O qO , oO _ qO C aO + C02 _ CaC03
= 38,1 + 213,7 - 92,9 = 158,9 J/K
AH = AHtc. 0 + M t.C ^K ,C C 0 3
= -635,10 - 393,50 - (-1206,90) = 178,30 kJ
^ 2 9 8 = ^ 2 9 8 ~TAS29g
= 178,30 - (298.158,9.10:?) = 130,90kJ
G ? 98 > 0 chng t 25c v latm s nhit phn CaCO
khng xy ra c.
III.8 . Tnh AS trong s trn 10g nc 0c vi 50g nc lng 40c trong mt h c lp. Nhit nng chyr.ca nc
334,4 J/g; T nhit ca nc l 4,18 J/K.g.
BI GII
Gi t l nhit lc cn bng nhit sau khi trn, ta c:
(10.334,4) + (10.4,18xt) = 50.4,18(40-t)
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T phng trnh ny xc nh c nhit cui cng sau
khi trn t = 20c
Gi ASj l bin thin entrpi khi chuyn lOg nc t
0c thnh nc lng 20c, ta c:
Gi bin thin entrpi khi chuyn 50g nc lng t 40c
xung 20c l AS->:
Bin thin entrpi trong s trn
AS = ASj + AS2 = 15,21 - 13,77 = 1,44 J/K
Vi AS trong h c lp bng 1,44J/K (AS > 0) chng t y
l mt qu trnh khng thun nghch nhit ng lc.
II.9. S g st din ra 25c. latm theo phng trnh
Vi nhit hinh thnh -824,2 kJ/mol.
Kt hp vi gi tr AS thu c bi tp (III.4) hy chng
t s g st l mt qu trnh t xy ra.
293
10 . 334,4 273
9QO+ (10-4,181x1 ) = 15,21 J/K.
9.73
29^= 50 X 418 ln = -13,77 J / K
' 313
phn ng
4Fe + 30 = 2 Fe93.
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BI GII
S g ca st ta nng lng di, dng nhit ra mi
trng xung quanh mt lng bng -824,2.2 ='-1648,4 kJ do
lm tng entrpi ca mi trng mt lng bng
0 _ 1 6 4 8 4 0 0 = 5529 J/K.** 298
Mt khc t bi tp (.4) ta c AS = -549,4 J/K
Vy ASlp = ASft + As = 5529 - 549,4 = 4979,6 J/K
AS^ lp > 0 chng t s g l qu. trnh t ph hy ca kim
loi iu kin thng v nhit v p sut.
111.10. Ti nhit no s chuyn lmol nc lng thnh
hi nc p sut kh quyn latm l mt qu trnh t din bin,
bit nhit ha hi lmol nc lng bng 40587,80J v b ii thin
entrpi ca s chuyn trng thi ny bng 108,68 J/K.
BI GII
Tiu chun nh gi chiu hng t din bin ca cc qu
trnh xy ra iu kin ng nhit, ng p nng lng t do G.
G = H - TS
AG = AH - TAS i vi qu trnh ng nhit.
Khi bay hi ca nc p = latm:
H20(Z) = H20(h)
AH = 40587,80J
AS = 108,68J/K
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Tac: AG = 40587,80 - T.108,68.
Hy tm nhit ! ti c cn bng lng - hi ca nc.
Mun vy hy cho AG = 0 do
40587,80 - 108,68T = 0 suy ra T = 373,46K
y l nhit si ca nc. iu kin nc lng
chuyn thnh hi ch xy ra theo mt chiu th AG < 0 . iu ny
- ^ V m 40587,80 0 ^0 ^s c thoa mn nu T > - > 373,46.108,68
IIL ll. i vi phn ng CO(k) +H20(k) = C02(k)+ H?(k)
Cho bit nhng gi tr ca bin thin entanpi v bin thin
entrpi chun 300K v 1200K nh sau:
AHgQQ = -41,16kJ /mol AH^qq = -32,93kJ / mol
a joq = -42,4W / mol Aj^QQ = -29,6kJ / mol .
Hi phn ng t din bin s theo chiu no 300K v
20K?
BI GIIA
Tnh A.G0 2 nhit da vo h thc AG = AH - TaS.
300K AG^ oo = -41160 - (300x -42,4) = -28440J.
1200K AGj200 = -32930 - (I200x - 29,6) = 2590J
Kt lun AGgoo < 0 vy phn ng cho t xy ra 300K
theo chiu t tri sang phi, song 1200K AJ9q0 > 0 phn ng
t din bin theo chiu ngc i.
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c. BI TP T GII
I.12. Tnh AS ng vi s nng chy lmol nc ti 0c, bit nhit nng chy ca bng 6 kJ/mol.
p s: 22 J .k ']
111.13. Trn 35g nc 250C (A) vi 160g nc 86c (B).
a) Tnh nhit cui cng ca h vi,gi thit l s trn
c tin hnh mt cch on nhit.
b) Tnh bin thin Entrpi ca A, B v ton b h.
p s': a) 75,lc '
b) A: 22,7J/K; B: -20,6J/K; h: 2,lJ/K
III.14- Tnh AS trong qu trnh un nng 1 mol hidro t
300 n 400K.
Bit rng vi Imol hidro; Cj, = 1,554 + 2}2.10"3T.J/K.mol.
p s': 1.74J/K i t
111.15. Hy tin on du ca ASgg v AHyg vi cc
qu trnh sau:
a) (C2H5)20 (1) - (C2H5)20 (k)
b) Cl2(k) -> 2C1 (k)
c) C10H8(k) -> C10Hg(r)
d) t chy (COOH)s(r) thnh COo(k) v H20 (Z)
e) C2H4(k) + H2(k) C2H6(k)
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III. 16. Tnh A; AH; AS vi qu trnh chuyn lmolH20
lng 25c v latm thnh lmol hi nc 1 0 0 c, latm , bit
Cp(H20 2) = 75,24J/K.ml v nhit ha hi i vi lmol nc bng
40629,6J/mol.
p SAH = 46272,6J/mol; AS = 112,95J/K AU = 4371,47.
111.17. Phn loi cc qu trnh cho di y thnh thun
nghch v khng thun nghch nhit ng:
a) S ng c ca nc 0 c v latm 'b) S ng c ca nc chm ng ti -10c v latm.
c) S t chy cacbon trong 0 2 c C02 ti 800K v latm.
d) S ln c ma st ca qu bng trn sn nh.
e) S gin n on nhit ca kh trong chn khng.
n i.1 8 . Tnh AS ca phn ng: N 2 + - H* = NH32 2
Bit s , = 191,489; = 130,586;
. Sj,H = 192,505J / K.mol
p S: l82,79J/k.mol
111.19. Mt s' vi khun trong t nhn c mt nng ^
lng cn cho s tng trng do s oxy ha nitrit thnh nitrat:
2NO aq + 0 9 = 2 NOg aq .
Bit rng s hnh thnh NO v NO3 , nng lng t o
chun tng ng bng -34,6 v -H0,5kJ/mol. Hy tnh nng
lng t do thot ra khi lmol NO b oxy ha thnh lmol NO3 .
p s: -75,9kJ
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IIIL20. Tnh nng lng t do hnh thnh chun 4^298
ca lmol H20 lng: H + O2 = H20 () bit 6.9,91;2 fyo
=130,684 v Sq = 205,38J/K.mol. Nhit hnh thnh
chun 25c ca Imol H20() bng -285,830 kJ/mol.
p s: -237,129 kJ/mol.
II.21. 0,35 mol kh tng 15,6c c gin n ng
nhit thun nghich t 1,2 lt n 7,4 lt n^r 0 Vv , & L A-
_ . J L 2 Y ' . ' A - a v V 'Tnh A/Q, AU,'/v4>(i vi qu trnh ny. 7
^ p s: -1530J; 1530J; 0; 5, 3J; -1530J
I.22. Tnh AGg73 ca phn ng: '
CH4 + H20(k) = CO + 3H2
Bit nhit hnh thnh chun AK^oggca CH4, H20(k) v
CO ln lt bng -74,8; 241,8 v -liO,5KJ/mo.
Entrpi chun ca CH4, H9(k) v c o bng 186,2; 188,7 v
197,6J/K.mol (Trong tnh ton gir thit rng AH v AS khng
ph thuc T). y
a) T gi tr AG tm c c tK kt lun g v kh nng t
din bin ca phn ng 373K. /
b) Ti nhit no th phn ng cho t xy ra iu
kin chun.
p s' AG = l,26.105J/raol; T > 961K
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111.23. Tnh AG ca s ng c -5c i vi nc lng
chm ng, bit rng AS ca qu trnh ny bng 21,3J/K.mol v
An0 = -5,8KJ/rrol ti nhit -5c. T kt qu tm -c, hy cho
bit v vic c hay khng trng thi cn bng gia nc lng v
nc -5c.
p s": AG = -92J/mol
111.24. a) Mt mol kh l tng gin 1 thun nghch nhit
ng lc t th tch 2 lt ti 20 lt- Tnh AS ca h v ca mi
trng xung quanh.
b) Cng 1 moi kh trn gin n ng nhit khng thun
nghch sao cho khng mt cng no c h thc hin. Tnh AS
ca. h v ca mi trng xung quanh.
c) Vi nhng kt qu nhn c t (a) v (b), hy chng t
, (bng con s" tnh ton) rng s nn t nhin kh l tng trong
h c lp s vi phm riguyn l II ca nhit ng lc hc.
p s a) ASh = 19,10J/K = -ASmt;
b) ASh = 19S10J/K, ASmt = 0
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Chng IV
CN BNG HA HC
TM TT L THUYT
1. iu k i n cn b n g n h i t ng. nh lu t t c dng khilng
iu kin tng qut v cn bng ca mt h nhit ng l
hm G ^ Gmin, AG = 0 T, p = const. Nu h nhit ng l phn
ng ha hc din ra T.p = const, gia cc cht kh l tng th
i vi phn ng tng qut:
+ V22 + ... vnAn = vjAj + v 2A 2 +. . . + v mA m...
p V j p V
AG = AG + RTln - ~ (1)P VI p v 2r A, -r A 2 -
vi Pi l p sut ring phn c^cc cht i trong phn ng
trng thi no v nhit v p Sut.
Khi cn bng c thit lp AG = 0, t (1) ta c:
p v pV2
AG = - RTin 77 -P V1 p v 2r Ai A 2 "*
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T.p = const; AG = const v t bng - RTlnKp. Vy:
p v l p v2
K = A' A;p P V1 p v2
r Ai A ,-(2)
Kp l hng s cn bng ng vi p sut l mt i lng hng nh mt nhit xc nh. Khc vi (1), (2rce gi tr p l p sut ring ng vi cn bng.
Biu thc (2 ) biu th thc cht ca nh lut tc dng khi lng do Guldberg v Waage thit lp.
Nu phn ng din ra th tch khng i th p dng phng trnh P = nv RT = CRT vo biu thc (2) ta s c biu thc hng s" cn bng ng vi nng K^ :
Cc i lng [ ] ng vi nng lc cn bng ca cc cht An v Am.
Cng nh Kp, Kc ph thuc nhit , khng ph tlmc nng .
Biu thc (3) cng c vn dng cho phn n^ ii n r:i trong dung dch lng tng.
vi dung dch khng l tng, nng Cj cc thay bng hot a. ' 1 ^
vi phn ng trong pha kh, hng s' cn bng cn c biu th qua nng phn mol Kx:
K = [ A i3 Vl. [ A 2 ]V2-(3)
(4)
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V i X- = - ; n; l s m o i c h t i .. 1 ZRi
Gia Pj v X c mi lin h Pj = P.X.
p = , p - l p sut ton phn ca h:
Gia Kp, Kc, Kz c mi lin h:
Kp = Kc.(RT)n =K x.PAn (5)
Vi An = ^ V m - ] T v n
2. nh hng ca n h t , p su t n cn bng ho
hc. N guyn l chuyn d ich cn bng ha hoc
a) nh hng ca nhit
Hng s cn bng Kp l mt hm ca nhit , m t s
ph thc n ta c phng trnh Vari't Hoff sau:
^ A H dlnKp/dT = = - (6 )
RT
Trong khong nhit t T! n T2 nu xem AH = const th sau khi ly tch phn, (6 ) tr thnh
Kp.T AH 1 1
ln K ^ = E (7)
S ph thuc ca hng sp cn bng vo nhit , .trong trng hp n gin, cn c biu th bng phng trnh c lin h n nhit AH v bin thin entropi AS ca phn ng
. _ AH AS ...ln.Kp = (8 )
p RT R
Phng trnh Van't Hoff dng (8 ) ng nghim ng khi
AH v AS khng ph thuc vo nhit
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b) nh hng ca p sut
T phng trnh lin h Kp v Kx ta c:
dlnK x /P= - = - ' (9)x p RT
T (9) thy rng hng s" cn bng Kx s thay i theo p sut T = const ty thuc vo s thay i th tch ca h \
c) S chuyn dch cn bng ha hc
Tho nguyn l Le Chatelier, khi lm thay i mt yu t"
no nh hng ti cn bng ha hc th v.tr ca cn bng s
chuyn dch theo chiu gim tc dng ca yu t" .
Xt yu t" nhit
T (6 ) thy rng Kp s ng bin theo T khi AH >0 (thu nhit). Vy i vi phn ng thu nhit, s tng nhit lm tng Kp tc to thm ra sn phm *
Xt yu t" p sut hay nng
T (1 ) -> aG = -RTlnK,, + RTln A'* p 1 p v 2
A ; r A -
t s" hng th hai v phi ca phng trnh bng i
lng RTlnQ. Khi : AG = R Tln-0-Kp
Du ca AQ c quyt nh bi t s: -Q -.
K P
Q < Kp AG < 0: Phn ng din ra theo chiu thun l chiu c tc dng lm Q tng ln cho ti khi Q = Kp th cn bang c thit lp.
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* Q > Kp -> AG > 0: Phn ng din ra theo chiu nghch l
chiu c tc dng lm Q gim xung tin ti bng Kp, lc ny
t ti s cn bng.
S thm mt kh tr vo h cn bng trong pha kh.
S c mt ca mt kh tr trong h cn bng lm. tng p
sut chung ca h, song v tr cn bng c thay i hay khng
cn ty thuc vo iu kin p sut v th tch ca h c thay
i hay khng.
* S thm kh tr V = const khng lm thay i trng
thi cn bng v p sut ring cc kh trong phn ng khng
thay i.
* S thm kh tr p - const c th lm bin i trng thi cn bng do s gim p sut ring cc cht kh trong h
phn ng.
3. Cn bng pha
a) Quy tc p h a Gibbs
y l mt nh lut quan trng nht ca cn bng ha
hc trong h d th m trc ht cn bng pha. Quy tc pha
c pht biu nh sau:
Bc t do V ca mt h cn bng, bng s" cu t c tr i s"pha p cng 2 :
V = c - p + 2 * (10)
Bc t do V cho bit s" cc thng s' c th thay i mt
cch ty (d nhin trong mt gii hn xc nh) m khng xm
phm vo cn bng pha ca mt h cn bng.
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- Th d xt Gn bng pha lng
-
B - BI TP C GII
rv .l . 1000K hng s cn bng Kp ca phn ng:
2S02 + O = ^ S 0 3 bng 3,5G a tm '1.
Tnh p sut ring lc cn. bng ca S0 2 v SO3 nu p
sut "chung ca h bng latm v p sut cn bng ca 02 bng 0 ,1 atm.
BI GII
Gi X l p sut ring ca S0 2 th p sut ring ca S O 3
b n g : l-P o 2 - X = 0,90 - X.
Gii ra ta c X = tm; v P0 = 0,33 atm.O i b l .
'X' IV.2. Tnh hng s cn bng Kp i vi phn ng:
N2 + 3H2 ^ 2NH3 25c
Bit: AG", ca NH3 bng -16,64 kJ/mol.
Kp s thay nh th no khi phn ng cho c vit
di dng: N 2 + - H 2 ^ N H 3 2 2
BI GII
AG - -2x16,64 = -33,28 kJ
A p 0
- AG = -R TlnK p > lnK p =RT
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-
-33,280 \ 8,314x298
InKp = ) = 13,43
Vy Kp = 6,80.10.
p 2NHs = K = 6,80.105
p N2 p h 2
t vi phn ng:
N 2 + -H 2^ NH3 25C2 2
Kp= f NH33 = # 7 =825
PN 'PHh 2
V.3. Mt bnh phn ng dung tch 1 0 lt cha 0,100 mo H2 v 0 , 1 0 0 moi I2,. 698K, bit hng s" cn bng Kc = 54,4.
Tnh nng cn bng ca H2, 12, v HI.
BI GII
H2 + I2 2HI
t = 0 0 , 1 0 0 0 , 1 0 0 0
t=toc (0 ,1 -x) (0 ,1 -x) , 2 x
(0,1 - x) (0,1-X ) 2s
10 10 10
K , . = - M - = 3 [[H2 ][I2]
= i M L -,0 ,1 - X ,0 ,1 -X . 0>'. '
10 ro
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-
p '= 7,38-=>x = 0,0787
(0 ,1 - x)
[I2] = [H2] = (0?~x) = 0,00213 mol/1 10
n 0 7 X 7[HI] = -= 0,0157 mol/l.
1 0
_____ Cn bng ca phn ng kh c 2 bng C:
^ c + CO2 2 CO
Xy ra 1090K vi hng SQ cn bng Kp = 10.
a) Tm hm lng kh c o trong hn hp kh cn bng, bit
p sut chung ca h l 1,5 atm.
b) c hm lng c o bng 50% v th tch, th p sut
chung l bao nhiu?
BI GII
C02 + c ^ 2CO n
Lc u 1 mol 0 .moi 1 mol
Cn bng 0s1\ 2 x mol 1 + x
Phn moi1 - X1 + X
2 x1 + X
nh lut tc dng khi lng c vit:
Kp=.-5S2_ = ^ c o l l _a2lL = p Pco2 p -x c o ,
1 + X*
10
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-
Suy r a x = 0,79. Vy hn hp lc cn bng cha 2 x = 2.0,79
= l,58mol CO v i - X = 1 - 0,79 = 0,21 mol C02 (8 8 % c o v 12%
C02 v s"mol cng nh v th tch).
tm p chung ti hn hp cn bng cha 50% v th
tch CO, ta vn dng nh lut tc dng khi lng:
T7- - Peo _ p-xo ^ Pco2 Xco
haylO = P ^ - p = 20 atm0,5
IV.5. Tnh AG v hng s cn bng K i vi phn ng
NO + O3 = n o 2 + o 2
Cho bit cc d kin sau:
n o 2 0 2 NO O3
AGh t W kJ/m olJ 51,79 0 86,52 163,02
AH^t 998 [kJ/mol] 33,81 0 90,25 142,12
ASht.298tJ/kmo1^ 240,35 240,82 210,25 237,42
ln ca hng s cn bng l h qu chu yu ca AH hay ca AS ca phn ng? Gii thch.
BI GII
Tnh AG ca phn ng:
AG u = Gt (N 02 ) + AGt (0 2 ) - AGt (NO) - AGt (O3 )
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-
Thay s" vo ta c A Gpu = -197,71 kJ
AG0 =HRTlnK, do suy ra
_ 1Q-A0/2.303RT
- 1 0 '197710/2303'S'314'298
K = 5.1034
xt nh hng ca yu t" nhit hay entropi, ta tnh
ring r tng i lng:
AH.u = AHt (N 02 ) + AH, (0 2 ) - AHht (NO) -AHht(0 3)
Thay bng s' ta c
AHU = -198,55J/K
ASpU = S(N02) + s(02) - S(NO) - s(03)
Thay bng s ta c
A Spy = -2,5 J/K.
T mi lin h gia hng s" cn bng K vi cc i lng
AH0 v AS0 ta c h thc l X
K= 1 0 +AS/2,303R 1 0 "AH/2,303RT
K = 100 i3.1034S
Bin thin entrpi ca phn ng r t nh v cu trc hnh
hc phn t ca cht phn ng v sn phm rt gn nhau. V
vy ng lc thc y phn ng din ra mnh lit t tri sang
phi l yu 0 nhit nng, v mt nng lng th sn phm bn
hn cc cht u.
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IV.6 . 25c phn ng
NO + - 0 2 = N022 2 2
C AG = -34,82 kJ v AH = 56,34 kJ. Xcjlnh hng s
cn bng 298K v 598K.
Kt qu tm c c ph hp vi nguyn l chuy dch cn
bng Le Chatelier khng?
BI GII
Tnh hng s" cn bng 25c bng cng thc
_^qAG/2.3RT
= 103482072,3.8,31.298
K = ,3.106
tnh hng s" cn bng K 598K, khng dng c cng
thc trn vi cha bit AG 598K. Tuy nhin nu chp thun
AH = -56,43kJ khng ph thuc nhit trong khong t 298 n 598K th c th vn dng cng thc
K2 = AH 1 1 . n K " R \ T2
trih hng s cn bng K? 598K. Thc vy
, K2 56430, i 1 ,in ~ ~ r = ----- (------------ ) suy ra
1,3.10 8,314 298 598
K2 = 1 2 . K < Kx: s tng nhit trong trng hp phn
ng ta nhit lm cn bng chuyn dch sang tri l ph.c tc
dng chng li s tng nhit l iu ph hp vi nguyn l Le
Chatelier.
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rv .7 . Xc nh nhit ti p sut phn li ca NH4CI l
la tm bit 25c c cc d kin:
AHgt [kJ/mol] A Gt [kJ/mol] ,
r H 4Cl(r) -315,4 -203,9
HCI(k) -92,3 -95,3
NH3 (k) -46,2 -16,6
BI GII
i vi phn ng
NH4Cl(r) = HCl(k) + NH3(k)
Hng s' cn bng
Gi T l nhit phi tm th vi p sut phn li l latm
ta c Phci = Pnh3 = 0,5atm do
= 0,5 X 0,5 = 0,25 (atm)2
AGggs ca phn ng bng
AG98 =-95,3 - 16,6 + 203,9 92kJ
T cng thc AG = -RTlnK ta c
92000 = -8,31 X 298 X lnK298 suy ra
' . 'V. 'Mt khc vi phn ng cho, A298 bng:
h 98 = -92,3 - 46,2 + 315,4 = 176,9kJ
_ * ! . ( J _ . )K298 2,303R 298 T
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-
lgKT-lgK 298 2,303x8,314 (298 t '
g0,25 + 16,12 = 78 0 ( - ) 2,303x8,314 298 T
T y tnh ra T = 597K.
IV.8 . Xc nh i lc ha hc ca st vi oxi ca khng kh
(Pq2 = 0.2atm) 1000K nu p sut ring ca oxi trn st (II)
oxit nhit ny bng 3.10' 18 mmHg.
BI GII
S oxi ha st l phn ng d th
2Fe + O2 = 2FeO
c hng s cn bng Kp = do lnKp = -ln P0p0 2
i lc ha hc c o bng cng cc i ca phn ng tc
l = -RTInPo- p sut ring ca oxi trong khng kh l "" - 2
0,2atm = 152mmHg.
3.1CT18p 2 152
Q 1 n~ 18A max = - 8,314 xlOOOx l n ---- = 376786J / mol
152
*TV.h 50c v di p sut l 0,334 atm phn ly a ca N20 4(k) thnh N 0 2 bng 63%.
Xc nh Kp, Kc, Kx.
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-
Ban u
Cn bng
Phn mol
BI GII
N20 4 ^ 2N02 n1 0 1
1 - a 2a 1 + a
1- a 2a1 + a 1 + a
P 2 ^ p 2 X2 P-X2 p . [ ] 2 K 2 ^ r -a N 0 2 = NOg _ 1 + q
p _ K N204 ~ P-XN204' _ XN204 ~ L:._ai(1 + (x)
Thay p = 0,344 atm; a = 0,63 vo phng trnh Kp, tm c Kp = 0,867 atm.
Kc = Kp.(RT)'in ; An = 2 - 1 = 1 do
Kc = 0,867(0,082.323)'1 = 0,034.
K* = Kp.p-An= = =2,52p 0,344
IV.10. T v p xc nh mt hn hp kh cn bng gm
3mol No, lmol H2 v lmol NH3.
a) Xc nh hng s" cn bng K ca.phn ng:
; N2 + 3H2 ^ 2NH3.
b) Cn bng s chuyn dch theo chiu no, khi thm
0 ,lniol N2 vo hn hp phn ng T,p = const
BI GII
XvH 2Kx= V - , % =8,33
v k x 5 5
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S thm N vo h T.p = const do Kx vn c gi tr
trc tc l 8,33.
Sau khi thm -0 , 1 mo N2> trc khi c s chuyn dch cn
bng th: - ' - ' '
Nh th Q > Kx v cn bng phi chuyn dch theo chiu no gim Q cho ti bng. Kx th cn bng mi s c lp
li. gim Q thi XN-t phi gm tc l cn bng chuyn dch
sang tri.
IV.11. 378K hng s' cn bng; Kp ca phn ng:
C2H6OH(k) ^ CH3CHO(k) + H2, bng 6.4.10'9. Nhit t
chy ca etanol v axetalehit l -1412 v -1196 kJ/mol.
Nhit hnh thnh ca nc bng -287 kJ/mol. Tm Kp ti
403K.
Chp nhn rng trong khong t 378 n 403K AH ca
phn ng l khng i, do vi dng phng trnh (7) ta c:
2
8,39
BI GII
lg K p .4 0 3 =
AH(403 - 378) + lgKp.378
2,303x403x378
A n 0 c xc nh theo nh lut Hess: /\
A AH .c.etanol - A H d.c.anehit AH ht.n
= -1412 - (-1196 - 287) = 71kJ.
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lgKp.403 = ----------------- --------------------(403-378) +lg(6,4 X 109)2,303 X 8,31 X 10" 3 X 403 X 378
Suy ra Kp 403 = 2?6.108.
IV.12. i vi phn ng N20 4k:) 2N 02, Kp 25c bng
0,144 v 35c bng 0,321. Tm AH, AS v AG 25c vi
phn ng cho.
BI GII
: K p .3 0 8 AH 1____ _K p . 2 9 8 2 , 3 0 3 . 8 , 3 1 2 9 8 3 0 8
Thay s vo, tm c
AH = 66,619 kJ.
AG = -RTlnKp = -8,31.298.1n0,144 = 4,8 kJ
AS0= AHi_AG!_= 6 M li_ 4 8 0 0 = 207i45J/K T T 298 298
IV.13. Cn .bng ca phn ng NH4H S ( r ) ^ NH3 + H2S(k)
c thit lp 200c trong mt th tch V. Phn ng cho l
thu nhit. Cho bit p sut ring c NH3 s tng, gim hay
khng i khi cn bng c ti lp sau khi: j'$>
a) Thm NH3; ( e r i
b) Thm H2S; ^ ' ***
- c) Thm NH4HS
d) Tng nhit ; ^ ^ ^ ^, s U\7r^,
e) Ap sut ton phn s tng do thm Ar vo h,
f) Th tch bnh tng ti 2V. f ' (cc V %>. 7.
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BI GII
a) Tng b) Gim
c) Khng i d) Tng
e) Khng i ) Tng.
IV.14. 0c v di p sut p = 1 atm phn y ca kh N20 4 thnh N 0 2 bng 1 1 %.
a) Xc nh Kp.
b) Cng ti 0c, khi p sut gii t latm xung 0 ,8 atm th phn li thay i th no?
c) Cn phi nn ng nhit hn hp kh ti p sut no
phn li bng 8 %.
BI GII
a) N20 4 ^ 2N02 Zn
t = 0 lmol 0 1
t = to f - a 2 a 1 + a
P2 f 2 a y\ l + aJ Tr 4a2 ^2 " I I ">Pmo \ 1 + a i 4(7- _
Kp Kp =P\T_n. ' _ ^ 1 tA 1 n'2*^4
1 + a
Thay a = 1 1 % v p = 1 atm vo phng trnh ny ta s c Kp = 0,049 atm.
4(X2 4 a 2b) 0,049 = r-.0j8 -^ = 0,0612
1 - a 1 - a
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Suy ra a = 0,123. phn li tng do gim p sut chung
ca h
4a2c) 0,049 = .p
1 - a
Thay a = 8 % suy ra p = 1,9 atm.
IV. 15. Tnh tc bin thin p sut theo nhit chuyn
pha i vi cn bng L ca H20 nguyn cht ti 0c, bit
AHnc = 6,01 kJ/mol;
VL = 0,0180 l.mol'1;
VR = 0,0196 l.mol-1.
BI GII
Phng trnh (1 1 ) i vi cn bng L c vit:
d P _ _AHn,c
dT Tnc.AVnc
Chuyn n v t Jun sang l.atm, ta c:
1 J = 9,87.103 l.atm
P ----6010.9,87.10~3 _ _136at K -1. T 273.(0,0180-0,0196)
Kt qu ny cho thy h nhit nng chy ca nc
xung 1K thi phi tng p sut cn bng n 136atm. T y suy
ra p sut tng ln 1 atm, th im chy ca nc gim i
7,35.10'3K, iu ny gii thch ti sao li c th trt trn bng
c.
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IV.16. Xc nh nhit bay hi ca Hg, bit rng ti 330c
p sut hi ca Hg bng 459,74mmHg v nhit ^si ca Hg
di p sut kh quyn l 357c.
BI GII
p dng cng thc (13) ta c:
In 76_0_= AH_ J _ 1_ A _ 5 8 1 5 kJ/moj459,74 8,314 603 630
IV. 17. Di p sut no, nc s si 97c?
Nhit ha hi ring ca nc bng 2254,757 kJ/kg.
BI GII
p dng phng trnh (13) ta c:
1 T> 1 T) A H , T g ~ T ^
g 1 " 2 " 2.303R T,.T2
lgp i = lg760_ i ^ 8 373-370
2,303x8,31 370 x373
= 2,8348 hay P = 683,6 mmHg.
c- BI TP T GII
IV. 18. 60K i vi phn ng:
H2 + C02. ^ , H 2(k) + C
Nng cn bng ca H, C9, H9O v c o ln lt bng
0,600; 0,459; 0,500 v 0,425 mol/1.
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a) Tm Kc, Kp ca phn ng.
b) Nu lng ban u ca H2 v C 02 bng nhau v bng 1
mol c t vo bnh 51 th nng cn bng cc cht bao
nhiu?
p s: Kc = Kp = 0,772;[H2] = [C023 = 0,106 M
v [H20] = [GO] = 0,094;
IV. 19. Mt bnh 51 cha lmol H(k), c un nng ti
800c. Xc nh phn trm phn li ca HI 800c theo phn ng 2 HI = ^H 2 + l 2(k). Bit Ko - 6,34.104.
p s': 4,8%.
TVO. 25c hng s' cn bng Kp i vi phn ng N2 +
3H2 2 N H 3 bng 6 ,8 .1 0 5.
a) Tnh AG ca phn ng.
b) Nu cng nhit trn, p sut u ca N2, H, NH3
l 0,250; 0,550 v 0,950 atm. Tm AG ca phn ng.
p s: a) -33,28 kJ; b) -25,7kJ
.rv^:. Ngi ta tin hnh phn ng:
PC15 ^ P C 1 3 + C12
vi 0,3 moi PC15; p sut u l 1 atm. Khi cn bng c th i t-
lp, p sut o c bng 1,25 atm(V,T = const).
a) Tnh phn li v p sut ring ca tng cu t.
b) Thit lp biu thc lin h gia phn li v p sut chung ca h.
p s': a) 0,25; p = p 0(l + a)
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IV.22. Xc nh nhit vi phn ng
' CaCO:^ Ca0 + C02
bit rng 800c p sut phn li bng 201,3mmHg v 900c
brig 992mmHg.
p s': -166,82 kJ/mol
IV.23. Trong mt th nghim ngi ta t mt mpun cha
N20 4 lng c m = 4,6g vo mt bnh phn ng ui ht khng
kh c dung tch 5,71. p v mpun ri a nhit ca bnh
phn ng ln 50C; Kt qu l N20 4 bay hi v b phn li, p
sut trong bnh o c l 0,4586^apn. Tnh phn li ca N20 4
v hng s" cn bng Kc vi phn ng N9O4 = ^ 2 N 0 2-
p s: 97,4%; Kc = 8,58
IV.24. Mt hn hp u gm 7% SO2, 11% 0 2, v 82% N*2
di p sut 1 atm, c un nng ti 1 0 0 0 K vi s c mt ca
mt cht xc tc. Sau khi cn bng c thit lp, trong hn hp
cn bng S0 2 chim 4,7%. Tm mc xy ha SO> thnh SO3 v
hng s" cn bng Kp v K ca phn ng 2S02 + 0 2;^ 2 SO3 (ghi
ch: mc oxi ha c o bng t s gia p sut cn bng v
p sut u).
p s': 32,9%; Kp = 2,44; K = 200
IV.25. Trong s tng hp NH3 400c tho phn ng N2
+ 3 H 2 ^ ^ 2 N H 3 , h n h p u g m N v H c l t h e o n g
t l hp thc ri a vo bnh phn ng dung tch 11. Trong hn
hp cn bng, ngi ta thy c 0,0385 mol NH3. Tnh K
-
IVJ26. Cho phn ng:
2N02 . ^ N 20 4(k); AH = -58,04kJ.
Hy tin on iu g xy ra cho h cn bng khi:
a) Tng nhit
b) p sut trong h tng.
c) Ar c cho vo h p = const v V = const
d) a cht xc tc vo h.
IV.27. 25c hng s'cn bng Kp ca phn ng thu
nhit 2NO + Br.?(k) ^ 2 NOBr(k) bng 116,6 atm*1.
a) Nu em trn NOBr c P=0,l08. atm vi NO c p =0,latm
v Br2 c p 0 , 0 1 atm to ra mt hn hp kh 0c th v tr '
cn bng s nh th no (cu tr li phi nh lng).
b) a NOBr c p = 5 atm vo bnh phn ng 50c th
thy trong hn hp cn bng c ^ p = 4,30atm. Tnh Kp
50c. So snh gi tr Kp ny vi Kp 25c. Gii thch?
p s: K p5()(,c = 179 atm"1.
TV28. Xc nh s" bc t do cc i ca h:
a) Mt cu t
b) Hai cu t.
c) Ba cu t.
IV.29. Xc nh s" pha cc i trong h:
a) Mt cu t.
b) Hai cu t.
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IV.30. Xc nh h nhit nng chy ca Cd 100 atm
bit nhit nng chy ring ca d = 57,32 kJ/kg; nhit nng
chy ca Cd di p sut kh quyn l 320,9C; Khi4ng ring
ca Cd rn v Cd lng bng 8,366 v 7,989 g/cm3.
p s: AT : 0,59
IV.31. Xc nh nhit chuyn pha t lu hunh rombic
sang u hunh n t ti 95,5c nu
AV = v n t - Vrombic = 0,014 cm3/g v dP/A = 25,5 atxn/K.
IV.32. Xc nh nhit ti Bi s nng chy di p
sut lOatm. Bit rng ti nhit nng chy l 271c, t trng
ca Bi lng v rn tng ng bng 10,005 g/cm3 v 9,637 g/cm3.
Nhit nng chy l: 54,392 kJ/kg.
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Chng V
DUNG DCH
A - TM TT L THUYT
1- Nhng tnh cht chung ca dung dch
a) Nng dung dch v cch biu th nng
Ngi ta gi ng cht tan trong mt n v khi lng
hoc trong n v th tch dung dch hay dung mi l nng .
C n h i u c c h b i u t h nng :
- Nng phn trm: c%
S" gam cht tan trong 1 0 0 gam dung dch.
Co = _________Sgam cht tan_________ 1 0 0S' gam cht tan + s gam dung mi
- S" gam cht tan 0 S" gam dung dch
-Nng moi:
S^ mo cht tan trong lt ung dch.
- Nng ng lng gam N:
S' ng lng gam cht tan trong mt lt dung dch.
- Nng molan m:
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S" mol cht tan trong mt kg dung mi.
- Nng phn raol Xi:
S" mo cht i chia cho s" mol ca cc cht c mt trong
dung dch.
Hai loi nng m v Xi hay c dng trong tnh ton
ho l vi chng khng ph thuc vo nhit .
b) nh ut Henry v tan ca cht kh trong cht lng.
Nu c l nng cht kh trong cht lng v p l p sut
r i n g ca kh th: c = k.p
vi k l h s" Henry, ch ph thuc vo nhit .
c) Cc nh lut v dung dch long.
- nh lut Rault: gim tng i ca p sut hi bo
ho ca dung mi trn dung dch bng phn mol cht tan:
*A *A _ n B = V------------T----- A r >
p n B + n A
- H qu ca nh lut Rault: S tng im si v s h
im ng c ca dung dch so Yi dung mi:
tng im si ( h im ng c) ca dung dch t l
vi nng molan ca cht tan:
At = K.m
vi K l hng s' nghir si hay hng s' nghim lnh.
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- nh lut Van Hoff v p sut thm thu 71 c,dung
dch: 7. V = nRT r '
Vi V l th tch dung dch
n l s" moi cht tan
R l hng s" kh
T l nhit tuyt i.
2. Cn bng ion trong dung dch
; - gii thch kh n n g dn in ca dung dch, Arrhenius
(1887) gi nh cht in ly (cht tan) trong dung mi thch
hp (nc chng han) b phn ly thnh cc ion dng v m.
Tu theo mc dn in ca dung dch m phn bit:
- Cht in ly mnh, phn ly hon ton thnh cc ion tri
du nhau mi nng .
- Cht in ly yu, phn ly mt phn thnh ion; kh nng
phn ly tng theo long.
Trng hp ny s phn ly l mt qu trnh thun nghch;
cn bng phn ly c thit lp trong dung dch gia phn t
khng phn ly v cc phn t phn ly (cc ion) l cn bng \ ion. Th d:
C H 3 C O O H ^ H+ + CHsCOCT
Fe(SCN)2+ ^ Fe3+ + SCN'
Kh nng phn ly c c trng bng in ly a.
_ S" mol b in lya = ----- : -
S mol ha tan
in ly a bao gi cung nh hn mt, ln hn khng:
0 < a < 1
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cl) p dng nh lut tc dng khi lng vo cn bng
ion. Khi nim v ch s'pK
n gin, xt cn bng ion sau nhit T "v .nng
c xc nh.
AB ^ A+ + B'
Nng u c 0 0
N n g c n b n g C ( 1 - a ) C a C a
Cn bng ion c c trng bng hng s'cn bng K.
TJr _ [A+] EB]K " ! AB!
Thay cc nng [A+], [B-] v [AB] bng cc i lng Ca
v C(1 - a), ta c: K =( 1 - a )
Biu thc ny cho thy a gim vi s tng ca c v c
gi l nh lut pha long Ostwald.
Trong tnh ton v cn bng ion, mt i lng hay c s
dng l ch s" pK: pK = -lgK.
Th d i vi cn bng:
C H 3 C O O H ^ H + + C H 3 C O O .
[H+] [CHoCOO- ] _RK = ----- 3 = 1,8.10 pK = 4,74
[CH3C00H] v -
H2S ^ E T + HS:
K = y n | p = 9 ,u o -s pK = 7,05L1 19J
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Cu(NH3)f- Cu2+ + 4NH3
[Cu2+] [NH,r _K = V = 4,6. Hr4 pK = 3,34
[Cu(NH3 ) f ]
b) Thuyt axit - baz.
Arrhenius
Axit l cht khi phn ly trong nc cho ion H+
Baz l cht khi phn ly trong
nc cho ion OH
Axit HA
Baz BOH
H+ + OH'
? B+ + OH'
Bronsted - Lowry
Axit l cht c kh nng cho proton trong dung dch
Baz l cht c kh nng nhn proton trong dung dch
A ^ B + H+
Axit Baz
A v B l axit v baz lin hp
c) Ap dng cc thuyt Arrhenius v Bronsted - Lowry vo
mt s'cn bng ion trong dung dch long nng ca nc
xem nh khng i bng 55,5 moi 1.
S phn ly ca nc: .
H20 ^ H+ + OH H20 + H20 ^ H30 + + OH\
Axit 1 Baz 2 Axit 2 Baz 1
K = m m = t H 3 ^ o = 10_16 2 5 0C
[H20] [H2 o ] 2
Tch s" ion ca nc:
K = [H+] [OH ] = [H30 +] [OH ] = 1 0 M pK = 14
(Arrhenius) (Bronsted)
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Lc Axit:
Baz:
HA ^ H+ +A" HA + H20 ^ H30 + + A".
Axitl Baz 2 Axit 2 Bazl
_ [H30 +][A~3 Ka [HA][H20] 55,5
Hng s" Axt:
_ [H-] [A-] _ [nsa*] [A-] _T^ _K^ ~ H A ] - [ H A ] PK = - ^ a
' Th d:
H2S ^ H * + HS' e s s + H ,0 Hao* + HS'
HCN ^ H+ + CN" HCN + H20 ^ H30 + + CN'
Axit cng yu, pK cng ln.
v axit mnh, phn .ly hon ton, khng c cn bng
phn ly nh khng p dng nh lut tc ng khi lng-
HC1 = H+ + Cl" HC1 + h 20 = h 30 + + c r
Theo Bronsted, Cl- l mt baz cc k yu, khng c kh nng kt hp vi proton.
-Lcbaz:
BOH =5=: B+ + OH" B + H20 .5^ BIT + OH .
bazl axit2 axitl ba 2Hng s^ baz:
K _ [B+ ] [QH~3 _ [OH~3 [BH*] b [BOH] B]
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Th d:
NH3 + H2.0 =5 ^ N H / + OH
baz axit axit baz
NH3 v NH4+ l mt cp baz axit' lin hp
OH' + HgO+ Ego + H20bazl axit2 axitl baz2
Lu rng vi cp axit, baz lin hp th:
Ka . Kb = Kw
3. Khi nim pH
pH ca mt dung dh l ogarit thp phn ca nng ion
H+ hay ion hironi H30*.
pH = -lg[H+] = -lg[H30 +]
i v i c n b n g i o n c a n c [ H + 3 [ O H ' ] = K W t a c :
pH = pOH = pKw = 14.
- Mi trng trung tnh 25c [H+] = [OH1 = 107.
pH = pOH = 7
- Mi trng axit [H+] > 1 0 7 ; pH < 7
- Mi trng baz [H+3 < 10 7 ; pH > 7
4. Gng thc tnh pH ca cc dung dch nc
- HA mt axit mnh nng C:
HA + H20 = H30 + + A
[HsO+] = [ A~ ] - c
pH = -lg[H30 +] = -lgC
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Cng thc ny ch ng khi pH < 6,5 v b qua [H30 +]
do nc phn ly ra.
- HA l mt axit yu c nng C:
pH == (p K a - lgC)
- B l mt baz mnh: B + H20 = BH+ + OH\
pH - 14 + lgC
- B l mt baz yu c nng C:
pH = 14 - (p K b - IgC)
- BA l mui ca axit mnh v baz mnh,
BA = B+ + A".
Cn bng ion ca nc khng b vi phm, do : pH = 7.
- BA mui ca axit yu HA v ba.z mnh.
BA = B+ + A" ; A + H20 HA + OH .
pH = 7 + (pKa + IgC) c l nng ca mu BA.
- BA l mui ca axit mnh baz yu c nng c .
BA = B+ + A" H20 + B+ ^ H30 ++ B
pH = 7 - (p K b - IgC)
- AB l mui ca axit yu HA v baz yu B c nng C:
AB = A~ + B+.
A" + H20 ^ HA-+ OH~ k*
B H + + H 20 ^ B + H 30 + Kb
pH = 7 + ( p K a -pK b)
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5. Hn hp m
Thng mt hn. hp m c to ra t mt dung dch
axit yu v mu ca axit yu hoc t mt dung dch baz yu v
mui baz yu.
Dung dch m c pH t thay i khi pha long hoc khi
thm mt lng va phi axit hoc baz vo dung dch. Mt hn
hp m gm axit yu c nng Ca v mt mui ca axit yu
nng Cm th:
pH = pKa + lg a -
Trng hp hn hp m ca baz yu nng C, v mui
ca n nng Cm th: pH = 14 - pKb - Ig-^53-c b
6. S thy phn ca mui
Thc nghim cho thy dung dch nc ca mt s" mui c
phn ng axit hoc phn ng baz.
Mui ca axit yu v baz mnh; c s thu phn ca anion.
Thuyt Arrhenius
A" + H 20 ^ H A + OH'
Hng s" thy phn Kh =
pH = 7 + ^(pKa + lgC)
K.
K.
Thuyt Bronsted
A" + H 20 ^ H A + OH'baz 1 axt 1
Kh = KVKa = Kh.
pH = 7+^(pKa+.lgC)
, c l nng mui (mol/I) Mu axt mnh v baz yu.
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Co s tKu phn cation
B+ + 2H20 ^ BOH + B+ + 2H20 BOH + H3Oh^ac axit 1 baz 1
Kh = Kw/Kb K K UK h =Kw Kh = ^ p ^ =
Cation l mt axit
KbK
pH = 7 - < p K a + lgC)2 p H = ( p K a -lgC)
M ca axit yu v baz yu.
B++ A- ^ BOH + HA B++ A '+ H ,0 ^ B O H + HAbaz axit ax itl bazo' 2 bazl axit 2
A ? .'?
Kh = H/Ka. K Kh = Kw/ K A2 .KB]
= KAi/KA2
pH = 7 + I (pKa - pKb) pH = ( pK Ai + pK A )
7. Tch s' tan
Xt cn bng gia mui kh tan trong dung dch v cc ion
ca mui: AnBm(r) ^ nA"q +.mB+q
p dng nh lut tc dng khi lng vo cn bng ny ta
c biu thc nh ngha tch s' tanT.
T = [A]n . [B+]m
[ A- ] v [B+] biu th bng mol/1
Ngi ta gi tan s (tnh b n g mol/I hoc g/1) l nng
c mui tan to thnh dung dch bo ha.
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1B- BI TP C LI GII
v . l . Ha tan 3,42g MgCl2; 2,63g NaCl vo 88,20g nc.
Tm nng % v khi lng ca NaC, MgCl2 v H20.
BI GII
Khi lng tng cng ca dung dch:
2,63 + 3,42 + 88,20 - 94,25g
Trong 94,25g dung dch c 2,63g NaCl vy nng %
VT l _ 2 >6 3 1 0 0NaC bng: ------ = 2,79%94,25
Nng % MgCl2: 3 ,4 2 10- = 3,63%94,25
Nng % HoO: 8 8 , 2 0 ' - 1 0 0 = 93,58%94,25
V.2. HN03 c nng 69% c khi lng ring l,41g.cm'3.
Tm th tch ca dung dch cha 14,2g HN03.
BI GII
Khi lng dung dich cha 14,2g HNO: = 20,6 g69
Th tch ca dung dieh s l: Q - = 14.6cm3 M1,41
V.3. Khi lng ring ca dung dch H2SO4 49% l
l,385kg/dm3.
Hi ly ba nhiu th tch ung dch H2S0 4 49% iu ch:
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a) 1 lt dung dch nng 0 ,5 N-
b) 400cm3 dung dch IN.
c) 250cm3 dung dch 0 ,2 M.
BI GII
a) MH so = 98.1I10 H9SO4 cha 2 ng lng gam.
98 )0,5N tng ng vi - - 24jTg H2S0 4 nguyn cht.
4
Th tch H2SO4 49% cn dng pha lt 0,5N l:
^ =4 99. . 36,lem49 . 1,385
Pha ong th tch ny bng 1 lt bng cch thm nc.
b) 400cm3 dung dch axit IN, cha:
^ = 19,6g axit nguyn ch't.1000
Vy th tch axit 49% cn ly pha 400cm3 IN l:
19,6 . 100 OQ 3 s 29 cm49 . 1,385 ^
c) 250cm3 dung dch cha: = 4,9g H2S 0 4
49y l lng H9SO4 cha trong: = lOg dung dch 49%.
4,9
, 10 qVy th tch phi ly: = 7,2em
1,380 ,
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QhxcQ-r/V.4. 45,20| ng tan vo 316g nc. Tnh im si, im
ho rn ca dung dch, bit cc hng s" nghim si, v nghim
lnh l 0,51 v 1 ,8 6
BI GII i '-
Nng moln ca dung dch l: = 0,418 . 342,3.316
ATs = K.m = 0,51 . 0,418 = 0,21
im si phi tm: > 373 + 0,21 = 373,2lK.
im ho rn: 2%* - (0,418. 1,86) = 272,2 2 K.C*c- c
V.5. S phn tch hemoglobin trong mu cho thy st
chim 0,328% khi lng,hemoglobin.
cOTm khi lng mol ti thiu ca hemoglobin.
^D ung dch nc cha 80g hemoglobin trong mt lt dung
dch c p sut thm thu bng 0,0260 atm 4c. Tm khi lng mol ca hemoglobin.
c) C bao nhiu nguyn t st c trong 1 phn t hemoglobin.
BI GII
a) Sc mol st c trong lOOg hemoglobin:
^ i = 5,87.1CT3 mol 56
Mt phn t hemoglobin phi cha t nht mt nguyn t
st; Vy trong lOOg hemoglobin s c 5,S7.103mol hemoglobin. Khi
vlng moi ti thiu ca hemoglobin:
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b) S" mol hemoglobin trong dung dch:
= V _ 0,0260 1 n _ R T _ 0,082. 277
= 1,14 10 3 mol
Khi lng mol: ------ -1,14 . 10^
T = 70200 g
c) Khi lng mol hemoglobin y so vi khi lng mol
ti thiu, thy gp 4 ln do phn t hemoglobin cha 4
nguyn t st.
V.6 . Tnh p sut hi ca dung dch ng cha 24g ng
(Cl2H22On) trong 150g nc 20c nu nhit ny p sut
hi ca nc nguyn cht bng 17>54mmHg.
BI GI
(17 5 4 -P ) __ =0,00833 => p = 17,39mmHg
17,54 5
V.7.'Dung dch axit xianhiric HCN nng 0,2M c hng
s Ka = 4,9.10'10.
Xc nh nng H30 + v in ly a
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BI GI
HCN + H20 ^ 0,2
0 ,2 - X
H3o + -+CN-0x_
0X
V Ka rt nh, HCN rt t in ly nn [H30 +] cng nh v
vy ly mt cch gn ng: X < 0,2; do 0,2 - X 0,2
- . 2
v = 4,9.1010 X = 9,9. 10-6 0 ,2 Vae;
c / -
_ 9 9 10-6 in ly a = 5 . cr0 hay 0,005%
v 0,2
V.8 . Cho 1 0 " 2 mol KSCN vo lOml dung dch mui Fe3+
nng 103M. Bit rng phc c to ra (mu sm) c cng
thc FeSCN2+, v nng ion Fe3+ t do, cha tham gia vo phc
l 8 -O^M. Tnh hng sbn ca phc.
BI GII
Xt cn bng to phc
Fe3+ +SN ^ FeSCNj+
lc u v 1 CT3 0
cn bng 8 .1 Q' 6 0,999. 0,001.
Hng s bn ca phc FeSCN2+ l:
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K = : --------- = ------- - --------- = 125[Fe ] [SCN-] 8 . 10 . 0,999
Ch : - nng u ca KSCN l 10"2/10' 2 = IM^ *
- Cn bng chuyn dch mnh sang phi v SCN d.
[FeSCN2'1'] _ 10-3
.9) Xc inh nng Cu2+ t trong 500ml dung dch
c iu ch t 0 ,1 mol CuS04 v 2 mol amoniac NH3.
Cho bit:
[CuNHs)]/" c hng sbn l 2 .1 0 13
Cp N H //N H 3 c pK, = 9,2.
S to phc xy ra theo phng trnh phn ng
Cu2+ + 4NH3 [Cu(NH3)4]2+
V cn bng NH3 + H20 NH4+ + OH" chuyn dch
mnh sang tri nn c th b qua tc dng ca NH3 vi H20.
Da vo y ta c nng cc cht lc u v lc cn bng nh
BI GII
sau:
Hng s bn ca phc [Cu(NH 9 ) 4 ]2+ c vit:
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V phc r t bn (K 1) nn c th coi X 1 . Mt cch gn
ng
ta c K * ----- ----- 5iL i------_ = 2.10 3.0,2(1 -x )(4 -0 ,8 x ) 4
Vy [Cu2*] = 0,2(1 - x) = 0,2/(3,2)4*.2.1013 = 9.5.10' 17
V.IO. Mt hn hp dung dch CH3COOH v NaOH c nng
(m ol/I) u t n g n g l a v X
Vit cc phng trnh cn bng axit - baz xy ra trong
hn hp.
T vic tnh hng s' cn bng, hy chng t rng phn
ng trong dung dch l hon ton. (Ka = 1 ,8 . 10'5X
Thit lp phng trnh pH ph thuc vo a, X, hng s" axit
Ka tch ion ca nc Kw trong 3 trng hp x < a , x = a v x > a
BI GII
a) CH3COOH + OH" ^ CH3C0 0 " + H20
H20 + H20 ^ HsO+ + OH~
CH3COOH + % 0 ^ CH3COO" + h 30 +.
b) Hng s" cn bng nhn c trong phn ng trung ho:
[CH3COCH [CH3COO-[H,Q+] Ka 1,8.10"
c [CH3COOH] [OH'] [CHgCOOH].! ^ icr14
Gi tr r t ln ca hng s" cn bng Kc chng t phn ng
l hon ton.
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c) d dng tm phng trnh pH, vi phn ng trung
ho axit yu bng baz mnh ta lp bng sau
CH3COOH + OH~ = CHgCOO + H 20
X < a a - X b qua X const
X = a x(l - a) x(l - a) ax const
X > a bo qua X - a a const
Trng hp X < a:
[HgO+] = -> pH = pKa + Colg(a - x) + lgxX
Trng hp X = a: [CH3COOH] = [OH" ] = K^H sO 4]
[CHgCOO-]* x(ci 1)
[HsO+] = - i - > p H = ( p K a + pKw + lgx)X 2
Trng hp X > a: [ OH- ] = X - a -> [H3O I = K ^x-a) - 1
pH = pKw + lg(x - a)
v.ir. Dung dch axt benzoic (axit yu) IM c cng pH vi dung dch HC1 nng 8 . cr3]^.
a) Tm pH.
b) Tnh hng s" axit Ka ca axit benzoic
BI GII
HC1 l axit mnh phn ly hon ton nn:
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[H30 1 = [ e r ] = 8.10'3 do pH = -lg8 .1 0 '3 = 2,1.
Axit benzoic C6H5COOH l axit yu, do trong dung dch
c cn bng.
C6H5COOH + H20 ^ H30 + + CgHgCOO".
[H30 +][C6H5C 0 0-] a [C6H5 COOH]
B qua s phn ly ca H2O nn [H3CT] = [C6H5COO"]
Vy: Ka = [H3OY = 8(.10r?) 2 = 6,4.10'5.
Y.I2 I Tnh pH ca dung dch NaCH3COO 0,1M, bit hng
s'baz Kb = 5,7.10'10.
BI GII
NaCHsCOO = Na+ + CH3COO"
CHgCOCr + H20 ^ CH3COOH + OH
0 ,1 0 0 V.
(0,1-x) X X
Kh = = 5,7JO10b (0,1-X) .
Mt cch gn ng 0,1 x.dp
X2 = 5,7.10"11 suy ra X = 7,6.10'6.
Gi tr nh tm c i vi.x p ng iu gi thit
X 0,1M.
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Vy [0H~ ] = 7,6.10"6M
[H+] = = 1 ,3 .1 0 _9M pH = 8,9 7 ,6 . 1er0
V.13. Tnh pH ca h m gm 0,050mol axit axetic v
0,050mol natri axetat trong mt lt dung dictu pH s thay i th f
no khi thm vo h m ny 0 ,0 0 1 ,mol HC1? 1 V V'~- ^ ^
BI GII
NaCH3COO = Na+ + CH3CpO"
CH3COOH + H20 ^ CH3 COO" + HoO+
[CH3 C0CT] [H3O ] *
a [CH3COH]
CH3COOH + Hao ^ CH3COO" + H3Oh
Lc u: 0,05 0,05 0
cn bng: 0,05 - X 0,05 + X X
K = 1,8 .1 o- 5 =(0,05 + x)x(0,05 - x)
. yAxit axetic l axit yu t phn ly nn: X 0,05. ^
0,05 - X 0;05 + X 0,05, o 1,8 . 10" =0,050
Vy X 1,8.IO"5 pH = -lgl,8.l0 ' 5 = 4,47
Khi thm HC1 vo h m th HO* do HC1 phn ly ra khi
phn ng vi CHgCOCP chuyn n thnh CH3COOH:
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H30 + + CHgCOO0^ CH3COOH + liso
Trc khi thmHCl-^OOC!)? 0,050 0,050
Sau khi thm: C/D o 0,05^0,001 0,05+0,001
Cn bng: X 0,049 + X 0,051 - X
Ka = l,8.icr5 = x(0,049 + ) => [H30 +] = Ka5-= 1,9;10-5 a (0,051 -x ) 3 a 0,051
vi X 0,049 X 0,051 .
pH = -