NHIT NG HC

I.

II.

III.

IV.
V.
VI.
VII.
VIII.

KH L TNG V THUYT NG HC CA CC CHT KH

1.
nh ngha kh l tng
2.
Cc nh lut ca kh l tng
3.
Phng trnh trng thi ca kh l tng
4.
p sut ring phn
5.
Gii thch phng trnh trng thi kh l tng trong thuyt ng hc
6.
Nhit dung v ni nng ca kh l tng
7.
Tc ca cc phn t
8.
Qung ng t do trung bnh
9.
Khng tuyt i
10.
Chuyn ng BROWN
TRNG THI LNG V LC CNG MT NGOI
1.
Cu trc ca cht lng
2.
Lc cng mt ngoi
3.
p sut d bn trong mt git nc
4.
Gc ni - nh lut JURIN
5.
nh hng ca cht ha tan i vi lc cng mt ngoi
6.
Lc cng mt phn gii
7.
Nc trong t
8.
Lc ht ca t v th mao dn
S THAY I TRNG THI LNG - HI
1.
S ha hi
2.
p sut hi bo ha
3.
Bin thin ca p sut hi bo ha
4.
m ca kh quyn
5.
Kho st s bay hi
6.
S si
7.
S ngng t trn mt thnh lnh - S ct
8.
S ngng t khi khng c thnh bnh
TRNG THI KT TINH V CC LC LIN KT
S NG C - S THNG HOA - S THN DCH HA
CC NGUYN L CA NHIT NG HC - NI NNG V ENTROPI
NNG LNG T DO V CC TH NHIT NG - CC P DNG
TRONG HA HC
P SUT THM THU CA CC DUNG DCH

BI TP

I. KH L TNG V THUYT NG HC CA CC CHT KH

1. nh ngha kh l tng:

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Ta ni mt cht kh trang thi kh l tng khi cc lc tng tc, lc lin kt gia

cc phn t (lc Van der Waals) hon ton bng khng. Cht kh cng gn trng thi

l tng khi mt ca n cng thp, ngha l khi p sut cng thp hay nhit cng
cao.

2.

Cc nh lut ca kh l tng:

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Cc cht kh him v hi kim loi l cc kh n nguyn t.

Khng kh l mt hn hp nhng iu ny ch thnh vn khi xt n n cc
tnh cht n hi ca n, do ta c th xem khng kh nh mt kh n gin c phn
t lng:

3.

Phng trnh trng thi ca kh l tng:

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Kt hp cc nh lut trn y ta c phng trnh trng thi ca cc cht kh l

tng:

4.

p sut ring phn:

5. Gii thch phng trnh trng thi ca kh l tng trong

thuyt ng hc

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Ngi ta cho rng cc phn t cht kh khng ngng chuyn ng hn lon.

Cc thnh phn tc ca mt phn t trn ba trc thng ging mt cch hon ton
hn n, i khi c nhng "va chm", khng c mt s tng quan no gia chng.
Cc "va chm" gia cc phn t l hon ton n hi, cng nh chuyn ng
phn t xy ra lin tc, vnh vin, m khng mt nng lng. (Cc nguyn l ng hc

ni rng chuyn ng vnh cu ca mt my c lp l khng th c c, nng lng

bin i dn dn thnh nhit. Nhng chuyn ng phn t ni y chnh l nhit).

6. Nhit dung v ni nng ca kh l tng:

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 bt k mt nhit no, CV v do U u khng ph thuc p sut ca

cht kh. l nh lut Joule. Mt cht kh l tng s khng tch ly th nng khi
b nn nh kiu mt cht rn. V trong cht kh l tng khc vi trong cht rn, cc
phn t khng tc dng vi nhau mt lc lin kt no dn xut t mt th. Mi cng
c hc cn thit nn mt cht kh l tng, do u xut hin di dng nhit.
Chng hn, gi s c mt cht kh cha trong mt xilanh c pittng v ta nn
kh bng cch dch chuyn pittng. Khi p vo pittng ang chuyn ng, cc
phn t chu mt xung v c gia tc. Do cc va chm, ng nng c a vo nh
vy s phn b cho tt c cc phn t; ni cch khc ton b khi kh nng ln.
7. Tc ca cc phn t:

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Tc bnh phng trung bnh ca cc phn t l:

Ta c th o trc tip cc tc trn, l cch xc nh bc ln ca khi

lng phn t.
Cc cht kh khuch tn qua cc thnh xp cng d nu tc cng ln v do
khi lng phn t cng nh (iu ny ch l ph v cc phn t rt b, kch thc
cc l xp thnh bnh ni chung rt ln so vi kch thc phn t).
8. Qung ng t do trung bnh

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Khi to ra chn khng, qung ng t do trung bnh tng t l vi. Vi mt

bn cnh qut n gin ta c th lm h mt cch d dng p sut trong bm xung
10-6 atmotphe. Nhng khi y qung ng t do trung bnh s vo c 1dm. Khi ,
cc phn t ni chung i t thnh ny sang thnh khc theo cc ng ng m khng
va phi phn t khc: p sut khng cn truyn mt cch bnh thng theo cc ng
ng v s hao ti tr nn rt ln. Do , "lm chn khng ", cn phi dng nhng
ng ng cng rng v cng ngn chng no th c th thc hin c cng tt.
9.Khng tuyt i

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V nhit tuyt i t l vi ng nng ca cc phn t cho nn n khng th m v

ngi ta khng th lm lnh mt cht kh xung di khng tuyt i 0 K = -273C,
nhit chuyn ng nhit hn lon dng li. Ngi ta s bin h cc cht
khng tuyt i u trng thi rn, s tht:
1)

Chng ta s thy rng mt cht rn t trong chn khng lun lun bay
hi v ngi ta t c mt s cn bng rn - kh.

2)

Trong cc cht rn, nhit tuyt i t l vi ng nng dao ng ca

cc phn t v khng th l m.

10. Chuyn ng BROWN

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Nm 1827 Brown, nh sinh vt ngi Anh quan st bng knh hin vi s

chuyn ng hn lon v khng ngng ca cc ht rt nh (ng knh nh hn 1(m)
trong cht lng, cc ht ny c gi l ht Brown v chuyn ng ca chng gi l
chuyn ng Brown. Qu o ht Brown l mt ng gp khc. Chuyn ng Brown
cng thy c khi kho st ca cc ht bi l lng trong cht kh.
V sao c chuyn ng Brown? l v ht Brown c kch thc rt nh nn
s va chm ca cc phn t vo ht trong cng mt khong thi gian ngn no theo
nhng pha khc nhau th khc nhau, hn na cc phn t n va chm vo ht theo
nhng pha khc nhau c th c vn tc khc nhau. Kt qu l xung lc ca cc phn
t tc dng ln ht theo pha ny c th ln hn hoc nh hn pha kia. V vy tng
xung lc ca cc phn t tc dng ln ht theo mi pha khng bng khng. Mt khc
khi lng ht Brown li nh, do di tc dng ca tng xung lc ni trn, cc ht
Brown s dch chuyn theo mt hng nht nh. Do tnh cht chuyn ng hn lon
ca cc phn t, tng xung lc tc dng ln ht Brown khng nhng thay i theo thi
gian v ln m c v hng tc dng nn qu o ht Brown c ng gp khc.
V l do trn ngi ta ni chuyn ng Brown phn nh chuyn ng ca cc
phn t.
II. TRNG THI LNG V LC CNG MT NGOI
1. Cu trc ca cht lng

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Trong cc cht lng, cc phn t nm gn nhau gp 10 ln so vi trong cc cht kh

p sut tiu chun nhng lun lun dch chuyn hn n theo cc hng do chuyn
ng nhit. Tuy nhin khng c s chuyn tip r rt gia trng thi kh v trng thi
lng, nhit ln hn mt nhit ti hn TC no : nu nn cht kh rt mnh

ta s thu c cht lng ch khng c mt lc no c hai pha (cc mi trng

ng cht) r rt: cht kh v cht lng. l trng hp nhit xung quanh, i
vi hli, hidr, nit hay xi.

Cc cht lng lun lun c mt s tnh cht khin chng gn vi cht rn ch

khng gn vi cht kh.
a)

Cu trc thng k: Cc kt qu thc nghim cho php ngi ta

quan nim

cc phn t cht lng to nn mt cu trc gn ging nh mng tinh th trong cht rn.
Tuy nhin i vi cht rn th cc ht to nn mng tinh th ch dao ng xung quanh
v tr cn bng (cc nt mng), nhng trong cht lng th mi phn t cng dao ng
xung quanh v tr cn bng nhng chng khng gn b vnh vin v tr y m "thnh
thong" li thay i v tr cn bng, di chuyn i mt on di vo bc kch thc
phn t. Khong thi gian m mi phn t c th tn ti mt v tr cn bng no y
s cng ln khi nhit cht lng cng thp.
b)

Lc gia cc phn t: Cc lc ht gia cc phn t (lc Van der

Waals) c

th b qua trong cc cht kh l tng v ch a vo vi hiu chnh nh trong cc cht

kh thc s tr nn rt quan trng trng i vi cc cht lng.

2.Lc cng mt ngoi

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Mt ca mt cht lng, ging nh mt mng n hi c xu hng thu v mt mt c

din tch cc tiu. Mt s th nghim v cc mng cht lng (hnh II.2 ) cho thy
iu .

a)

Mt mng nc (c thm mt cht ty lm cho mng bn hn) c

t

trn mt ci khung c mt cnh (mt cng rm) di ng c. Cn phi tc dng mt

lc ln cng rm ngn khng cho n quay theo chiu mi tn.
b)

Mt mng nc khng tc dng mt lc no ln si ch vt qua n (hay

ni

chnh xc hn, n tc dng hai pha ca si ch nhng lc cn bng nhau). Nhng

vng ch s cng thnh vng trn nu ta chc thng mng nc bn trong.

3.p sut d bn trong mt git nc

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Trong cc th nghim k trn, khi gii hn ca mt dch chuyn mt khong dx, cc

lc cng mt ngoi thc hin mt cng:

Nh vy th nng mt ngoi ca mt mt c din tch S c ln l A.S. N

c xu hng ly gi tr cc tiu; khi nh hng ca trng lc c th b qua mt khi
cht lng do s c dng hnh cu.

4.Gc ni - nh lut JURIN

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Khi tip xc vi mt mt rn, cc cht lng c th t nhiu b hp th hoc t nhiu b

y ra.

Do hin tng trn, mt thong ca mt cht lng trong mt ng khng phi l

mt mt phng m l mt mt khum.
Cc lc cng mt ngoi gii thch s li ln hay lm xung ca mt khum
trong cc ng, c bit l trong cc ng mao dn (hnh II.5 ). T i khi ngi ta
dng t lc mao dn gn cho lc cng mt ngoi.

5. nh hng ca cht ha tan i vi lc cng mt ngoi

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Nng ca cc phn t trong cht b ha ha tan trn mt mt dung dch

khng ging nh bn trn mt dung dch. C nhiu cht, c bit l cc cht
in phn chy khi mt thong v do lm tng lc cng mt ngoi ca
dung dch ln i cht (hnh II.6a).

Tri li, cc cht khc (x phng, cht ty, protein...) tp trung trn mt v v
th lm gim lc cng mt ngoi (cht hot ng mt ngoi) (hnh II.6b).

Tnh hot ng mt ngoi ca cc axt bo tng rt nhanh cng vi s nguyn

t cacbon trong phn t. ng thi cc axt bo cng kh c th ha tan.

Mt mng nc ph mt mng khng bay hi nh th s rt bn: nu mt ch

rch xut hin trn mng, lc cng mt ngoi ca vng cn li ca mng s mnh hn
v cc mp ca mng s khp kn li. Chnh v th cc cht c tnh hot ng mt
ngoi lm cho mng cht lng, cc bong bng v cc bt si tr nn bn vng.
6.Lc cng mt phn gii

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7.Nc trong t

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Nc c th lp y tt c cc l nh trong t; khi ta t ti mt nng sut cc i

ca t. Nu c nhiu nc hn, cc ht t s tch ri v t mt ht rn chc (ct
chy, dng bn, tuyt "ra nt").
Nu c t nc hn, khng kh s chim mt phn cc l nh trong t: iu
ny l cn thit cho s sng cc vi khun trong t, m cc vi khun y li cn thit
cho thc vt. Cn phi c t 6 n 10% khng kh trong t (tnh theo th tch) cho
cc loi rm c ca gia xc, 10 n 15% cho cc loi ng cc, 10 n 20% cho c ci
ng.
Khi phn t ang xt nm xa lp nc ngm v vng nc dng theo mao dn
nh ln trn phn t , mt phn ln nc c trong t ( chng hn do ma hay do
ti) s chy di tc dng ca trng lc. Ngi ta gi phn nc ny l nc trng
lc (adose water) hay nc t do theo cc nh nng hc. Chuyn ng ca n gi l s
thm (percolation).
Nhng, mt khi phn nc ny chy i, cc mng nc c lp vn cn li
hoc xung quanh cc ht t, hoc ch tip xc gia cc ht t, c gi li bi
cc lc cng mt ngoi. Phn nc c trong t ny c gi l nc vng v gi tr
cc i ca n, khi qu trnh thm dng li, gi l nng sut gi ca t.
Nng sut gi ny c th o nhanh chng, bng cch quay mt mu (nu
khng th phi i 48 gi). N c gi tr (tnh theo trng lng v c qui v t kh)
khong 10% trong ct th, 15 n 30% trong bn v 40% trong t st. ( thu c
gi tr tnh theo th tch ta cn phi nhn ln vi t trng biu kin ca t kh, t trng
ny c th thay i t 0,8 n 1,3). V cc xp thng thng (t s th tch cc l
nh v th tch ton phn ca mu) vo c 40% cho nn ta thy rng trong loi t st
cht st, nng sut gi gn t nng sut cc i: khng cn ch cha khng kh.
Cy ci ch c th ht c mt phn nc vng ny, phn cn li b hp th
bi cc ht t, ngha l b gi li bi lc Van der Waals. Gii hn ca phn nc ny
gi l im cn. N vo c 1% trong ct th, 5 n 15% trong bn, 20% trong t
st v 50% trong than bn.
8.Lc ht ca t v th mao dn

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Cng ging nh trn, nc vng trong t c dng thu knh hai mt lm gia
cc ht t (hnh II.7b) s tc dng ln nc mt lc ht. Theo l thuyt, ta c th o
lc ny bng cch lm nng ct nc nh dng t (hnh II.8a). V gp cc di
khng t c v c th thc hin ti ch trn mt t, ngi ta s dng my
Bordas - Mathieu (hnh II.8b) trong t lm nng ln khng phi mt ct nc, m
l mt ct thy ngn. Thot tin, cho tc dng mt lc ht ln hn gia 1tr cn bng,
ngi ta t ti trng thi cn bng trong vi gi. Khi cc lc ht ln hn 1 atmotphe,
ngi ta dng cc hin tng nghim lnh hoc trng lc.

Khi cc loi t c kch thc ht khc nhau tip xc nhau, s xy ra nhng

qu trnh trao i nc di dng hi, v v lu di th mao dn s tr thnh ging
nh nhau i vi tt c cc loi t. Nhng khi m ca cc loi t khc nhau
khng phi nh nhau: t cng mn, hm lng nc ca n cng ln.
III. S THAY I TRNG THI LNG-HI
1. S ha hi

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Ngi ta gi trng thi kh ca mt cht lng hay cht rn nhit bnh

thng l hi, s thay i trng thi lng - kh v vy gi l s ha hi. C hai dng
bay hi chnh: s ha hi xy ra trn b mt ca cht rn hay cht lng bt c
nhit no (s bay hi), v s bay hi xy ra trong lng cht lng mt nhit gn
nh c nh di mt p sut cho trc (s si).
Trn mt cht lng, mt s phn t thot khi lc gia cc phn t v chuyn
sang trng thi kh. V chng l nhng phn t nhanh nht, nng nht ri khi cht
lng cho nn cht lng b ngui i. Mt phn ng nng ca cc phn t ny dng
thng th ca cc lc gia cc phn t v trng thi kh, cc phn t ny s t nng
hn so vi trng thi lng. Cui cng s ha hi ca mt phn t c chuyn
thnh s hp th
nhit. Nhit hp th bi mt gam cht lng ha hi gi l nhit
ho hi. Di y l mt vi gi tr:

2. p sut hi bo ha

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3. Bin thin ca p sut hi bo ha

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p sut hi bo ha tng cng nhanh cng vi nhit theo mt qui lut rt

phc tp.

4. m ca kh quyn

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5. Kho st s bay hi

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Chng ta hy ly trng hp mt lp nc hay mt lp t bo ha nc bay

hi vo khng kh t do. (Cc lp lun ca chng ta vn c gi tr trong trng hp
s ngng t, nhng khi cc i lng c xt tr nn m). Nhit cn thit cho s
bay hi c th ly t ba ngun:

6. S si

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Ni chung cht lng c cha mt lng khng kh ha tan. Khi un nng cht
lng, lng khng kh ny thot ra, v tnh ha tan gim cng vi nhit . Trn thnh
bnh cha s xut hin cc bt khng kh, bn trong cc bt s xy ra hin tng bay
hi.
Do hin tng ni trn, p sut trong cc bt tng ln v chng tch khi thnh
bnh. Chng bin mt khi i n cc vng lnh hn (chnh lc m un nc ''reo'').
n mt lc no nhit bn trong cht lng s cc bt kh to ra khi i ln v
v ra trn mt: l s si.

c bit, nu cht lng c loi kh cn thn bng cch lm si trc trong

mt thi gian di ta s thy mt s chm si. Khi y ch cn cho vo mt s ht thy
tinh chng hn khng kh c hp th trn b mt th hin tng si s khi pht.
Cc ht ion ha cng c tc dng nh vy. l nguyn tc bung bt trong
vt l ht nhn.
Nc cha trong ni hi, mt ni supde c th khng si, d nhit cao th
no. p sut bn trn cht lng bng p sut hi bo ha cng vi p sut ring phn
ca khng kh cha bn trong , do n lun lun ln hn p sut hi bo ha. Mt
s si bng s xy ra, nu ta cho kh thot ra ngoi.
Hin tng si cng xy ra khi ta lm lnh cc thnh bnh (th nghim lm si
ca Franklin). Khi y nhit khng ng u, v nh chng ta s thy, c s ct.
7. S ngng t trn mt thnh lnh- s ct

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Nh vy, h cha mt cht lng ch trng thi cn bng khi cht lng ny
c ct hon ton qua phn lnh nht ca h (nh lut thnh lnh do Watt, ngi
pht minh ra my hi nc pht biu).
Hin tng ct c s dng lc cc cht. tin hnh nhanh chng, ta un
nng cht lng hay h p sut khng kh bng mt bm chn khng hoc tin hnh
ng thi c hai cch cho n khi thy si. Nhng s si khng phi l nht thit phi
c. Mi ngi u quan st thy hin tng ct nc nng t hoa sen chy trn
thnh lnh ca ca bung tm.
8.S ngng t khi khng c thnh bnh

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Chng ta ch nghin cu s ngng t ca hi nc trong kh quyn l hin tng c

bit r nht. khi nhit h xung, p sut hi bo ha s tr thnh thp hn p sut
ring phn ca hi nc, hi nc s trong mt trng thi cn bng gi. Ta c qu
bo ha. Nhng mt cch t ng khng c s xut hin mt git nc nh.
Tht vy, Kelvin chng minh rng p sut hi bo ha bn trn mt git
nc nh bn knh r khng phi l P, m l :

S qu bo ha cn phi vo c 600% cc git nh xut hin mt cch t pht.

Trong thc t ta thy xut hin cc git nh c s ngng t, do cc nhn

ngng t. Cc nhn ngng t c th l:

IV. TRNG THI KT TINH V CC LC LIN KT

1. Cc tnh cht ca trng thi kt tinh

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Khi lm lnh mt cht lng tinh khit xung di mt nhit xc nh, n s

ng c. Nu s ng c xy ra kh chm, ta thy xut hin cc cht rn gii hn
bi cc mt phng nh. l cc tinh th.
(Ngi ta cng c th thu c cc tinh th bng cch bay hi chm dung mi
ca mt dung dch, hay bng cch lm lnh nu cc cht d tan khi nng hn l khi
lnh. Trong nhng trng hp ny hnh dng ca tinh th ph thuc vo bn cht ca
dung mi).
Dng ca tinh th ph thuc vo cht tinh khit m ta xt v iu kin hnh
thnh. Ni chung, tt c cc tinh th thu c i vi mt cht tinh khit cho u
ng dng v phng din hnh hc nh cc php tnh tin n gin i vi cc mt.
S pht trin ca cc tinh th khng xy ra vi cng tc theo tt c cc
hng. Do ta c th to ra nhng tinh th hnh kim, i khi c cc nhnh (tinh th
cy). Nu s ng c tip tc, cc tinh th s gp nhau v ngn s pht trin ca
nhau. Mt phn cch gia cc tinh th (ngi ta cn gi l cc vi tinh th) ca a tinh
th hnh thnh nh vy, khng cn l mt phng na.

Th d: Khi nc ca bng h tan ra di nh sng mt tri, cc mt phn

cch chy ra trc tin. Kch thc ca cc tinh th nc c th t ti nhiu
xentimt, hnh dng ca chng khng hon ton u n.
S tn ti cc mt phng c to thnh mt cch t pht do khng cn c
trng cho trng thi kt tinh.
Trng thi kt tinh c c trng bi:
a)

Mt nhit nng chy kh xc nh v l hng s i vi mt cht tinh

khit cho.

b)

Tnh d hng trong phn ln cc tnh cht ca chng, ngha l cc tnh

cht ph thuc vo hng:
b1) bn c hc khng nh nhau theo tt c cc hng.

b2) Moul Young (sut Young) ph thuc vo hng theo ta ko

tinh th, dn nhit ph thuc vo hng ca thng lng nhit, dn in ph
thuc vo chiu dng in, chit sut ph thuc vo hng tia sng (i khi nhng
tnh cht d hng ny khng th hin i vi mt s tinh th, nh cc tinh th lp
phng.
b3) Tnh chng n mn (mui ha tan c b nc n mn, kim loi b
axt n mn) ph thuc vo mt gii hn tinh th. Nu l mt mt t nhin th n
chng n mn tt hn so vi mt mt phng to thnh bng nhn to.
b4) Khi kho st nh sng phn cc, chng ta s thy rng nh sng
ny b bin i khi i qua mt bn tinh th, s bin i ph thuc vo hng ca tinh
th i vi mt phng ca bn mng. iu ny cho php ta bit mt ming c v
ng nht thc ra l mt a tinh th.
2. Cu trc ca cc cht kt tinh

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Cc tnh cht k trn v mt s cc tnh cht khc c gii thch bng s kin
cht kt tinh c to nn t mt mt s sp xp cc nguyn t, mt kiu c lp i
lp li mt cch tun hon theo ba chiu to nn mt s "lt gch" u n trong
khng gian, t u ny n u kia ca tinh th.
"Vin gch lt" (phn "lt" nh nht) c gi l nguyn t. Ni chung l
mt hnh hp. Tp hp cc ny lp thnh mt mng khng gian v nh ca cc l
nhng nt mng.
Ngi ta phn bit 14 kiu mng tinh th, chng ta ch nu ra y 3 kiu
thng gp nht trong s cc cht n gin.
a)

Mng lp phng tm khi: nguyn t l mt khi lp phng v

nu c mt nguyn t mt nt th s c cc nguyn t cng loi tt c
cc nt khc v tm ca cc khi lp phng.

(Khng nn v th m cho rng cc tinh th t nhin ca kim cng hay st l

cc khi lp phng).
b)

Mng lp phng tm mt: nguyn t l mt khi lp phng. Nu

c mt

nguyn t nm mt nt th s c cc nguyn t cng loi tt c cc nt khc v

tm cc mt ca khi lp phng.

c) Mng lc gic: nguyn t l mt khi lng tr thng c y l mt lc

gic u. Nu c mt nguyn t mt nh th s c cc nguyn t cng loi mt
nh khc, tm ca cc lc gic v tm ca ba khi lng tr y hnh thoi, ba khi
lng tr ny l do s phn tch cc nguyn t m ra.
Th d: Co, Mg, Zn, Cd, nc , than ch.
3. Cc tinh th kim loi

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Chng ta u bit rng cc kim loi cha cc electron t do dch chuyn. Ta c th

xem cc nguyn t tr thnh cc ion dng, khi mt mt hay nhiu cc electron v cc
electron to thnh mt "kh quyn" trong khong gia cc nt. Nhng cch nhn ny
khng chnh xc v qu n gin, v mt nguyn t kim loi khng h c tnh cht ca
mt ion tng ng: tnh ha tan, bt thn c mu, cc kch thc. L thuyt v trng
thi kim loi rt phc tp, chng ta khng cp y.
4. in ha tr v cc tinh th ion

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Trong nhng tinh th ion, cc nguyn t bin thnh cc ion dng hay m xen ln
nhau, v s c kt l do s ht tnh in gy nn.
Th d: NaCl.
Nu xem cc ion nh l nhng qu cu tip xc vi nhau, i vi mi ion ta s
tm thy mt bn knh, gi nguyn khng i, khi ta chuyn t hp cht ny sang hp
cht khc. Cc catin c bn knh nh hn bn knh ca nguyn t kim loi tng ng.
Cc catin ni chung c bn knh in ln hn so vi cc catin.
Cc gi tr ca bn knh theo angstrom:

Dng lin kt trn y gi l in ha tr. Nguyn t clo c ha tr mt, ngha

l n ch c th bt ly mt electron. N c bao quanh bi su nguyn t natri, v ta

ch c th ni rng bng cch ny hay cch khc c bit hn n cung cp cc

electron ca mnh. Trong cc tinh th ion khc, ion clo c th c bao quanh bi mt
s cc cation khc: 8 trong CsCl. Cc im ha tr khng c mt hng u tin no.
5. Tnh cng ha tr v cc tinh th cng ha tr

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Th d: kim cng.

Lin kt cng ha tr mnh hn lin kt ion rt nhiu: on cc electron ca hai

nguyn t ghp vi nhau bng cch thm nhp vo nhau. Khong cch gia cc
tm nh hn. Nhng, lun lun coi nhng nguyn t nh nhng qu cu tip xc
nhau, ta c th nh ngha bn knh cng ha tr ng ch l khng i t hp cht
ny sang hp cht khc. Bn knh cng ha tr r rng l b hn bn knh ion tng
ng.

6. Lin kt Hydro

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Cc nguyn t c tnh m in cao nht F , O , N v Cl (theo th t gim) u c th

ht cc nguyn t H, mt bn cc ha tr ca F, O, N hay Cl u bo ha.
Chng hn, ta s c cc lin kt biu din bng cc ng chm chm gia hai
axt bo.

Cc lin kt hydro c mt rt nhiu trong sinh ha. Chnh cc lin kt ny ghp

cc phn t ca pliscart trong xenlul hay trong cc mch peptit trong protein.
7. Cc tinh th phn t

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Trong cc tinh th phn t thng gp nht trong ha hu c, cc phn t gi c

tnh ring bit ca chng. Chng c gn vi nhau bng lc Van der Waals. Nng
lng lin kt cn yu hn na, vo c 1kcal/mol.
Chnh lc Van der Waals gii thch s hnh thnh cc hirat.
V. S NG C, S THNG HOA, S THN DCH HA
1.S nng chy ca mt cht kt tinh

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Mt cht kt tinh nng chy mt nhit kh xc nh khi hp th nhit (nhit nng

chy). im nng chy rt d thay i cng vi p sut theo cng thc Clapeyron
tng t nh cng thc i vi s bc hi:

2.S ng c ca mt cht lng

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Khi ngi ta lm lnh mt cht lng xung di im nng chy, s kt tinh khng
xy ra v chuyn ng nhit chng li s sp xp c trt t ca cc phn t. Ta c hin
tng chm ng.
S chm ng dng li di mt nhit no ph thuc vo cc mm
ngng t (cc loi bi l lng) nm trong cht lng. Ta d dng quan st thy s
chm ng trong cc ng mao dn, bn trong cc ng ny khng c cc mm ngng
t ca kh quyn. Cc git nc nh hon ton khng c cc mm ngng t chm
ng n tn -400C, sau nhit ny chng ng c mt cch t pht.
S chm ng dng li, s ng c s gii phng nhit v nhit lm tng
nhit ln n im nng chy v s ng c tip tc din ra nhit ny (hnh
V.1).
3. Trng thi thy tinh

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C th xy ra trng hp s chm ng xy ra ln n mc cc phn t mt ht tnh

linh ng, khng th no i ra khi ci "by" to ra bi cc phn t bn cnh. Khi y
ta quan st c s ng c t t v cui cng i n mt cht thy tinh. Trong
trng thi thy tinh, cc phn t khng sp xp u n, mc d n c mt trt t cc
b no .
Khc vi cc cht kt tinh, cht thy tinh c tnh ng hng t ra l khi ngi
ta khng tc dng ln chng cc ng sut c hc. Khi nung nng, cc cht thy tinh s
nng chy nho (s "nng chy nho" cng c th l do cht y l mt hn hp:
l trng hp cc cht bo hay st c to thnh t mt hn hp gm hai bin th
th hnh, st v st ().
Cc cht thy tinh khng lc c, cng khng c cc mt phng trt. Ch
v l mt ng cncic.
Ngi ta quan st c trng thi thy tinh hu ht sau mt qu trnh lm lnh
rt t ngt. Mt s dung nham c lm lnh rt t ngt s to ra thy tinh: l
cc pxiin.
Nung nng knh ca hay thy tinh silic trong mt thi gian di n mt nhit
, chng gi trng thi nho, ta c th lm pht trin cc tinh th. Chng tr nn
c hay d v.
4. S ng c ca mt hn hp

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Khi lm ng c mt hn hp gm hai cht tinh khit khng ha hp c vi nhau,

hai trng hp gii hn c th xy ra:
1)

Hnh thnh cc tinh th hn hp cha hai cht tinh khit vi t l c th

bin i. Ngi ta ni rng c hin tng ng kt tinh v ta thu c mt
dung dch rn.

2)

Thot u ch c mt trong hai cht tinh khit ng c. Cng c th xy

ra nhng trng hp trung gian.

5. Cc dung dch rn

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Khi lm lnh mt hn hp gm hai cht tinh khit c th ng kt tinh, thnh

phn cht rn, mt nhit cho, khc thnh phn ca cht lng. Hn hp cng
nhiu thnh phn cng kh nng chy. Th d nh trn hnh V.2, trn ta t cc
chun trn trc honh v cc nhit trn trc tung. (Chun l t s gia khi
lng mt thnh phn v khi lng tng cng).

C nhng trng hp cho n cng ngi ta khng lm ng c c thnh

phn d nng chy nht, nhng lm ng c c mt dung dch rn P no d
nng chy hn cc thnh phn ly ring. l trng hp hn hp NaCl, LiCl (hnh
V.3).
6. S kt tinh ca mt hn hp khng to ra dung dch rn

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7. Php nghim lnh

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Khi mt cht ha tan mt lng nh khng ng kt tinh vi dung mi, ng

lng k t im ng c vi dung mi tinh khit c th xem nh mt ng thng:
h im ng c ca dung mi t l vi s mol ha tan trong mt gam dung mi.
Nh nhit ng hc, ngi ta chng minh c h thc sau y, ch ng i
vi cc dung dch long:

8. S thng hoa

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Cc cht rn bay hi lin tc b mt cc phn t mt ngoi cho n khi p sut hi

bo ha, cng ging nh cc cht lng. Ngi ta gi hin tng bay hi ca cc cht
rn l s thng hoa. Ap sut hi bo ha ca cht rn thng rt nh, nhng trong
trng hp naptalen (C10H8 naptalin cc hiu thuc) ca it hay nc , p sut
vo khong nhiu mmHg nhit xung quanh.
Khi p sut hi bo ha ca cht rn ln hn p sut kh quyn (oxt asen trn
4000C, tuyt cacbonc nhit bnh thng), ta khng thy c g ging nh hin
tng si. Do p sut hi bo ha khng th t c ch tip xc vi cht rn, s
thng hoa ch c th xy ra rt nhanh v ton b.
Ap sut hi bo ha trn cht lng chm ng ln hn trn cht rn khi chng
cng mt nhit . Nu trong mt m my cc git nc chm ng xut hin cc
vi tinh th nc , nc s ct thnh cc git nh trn cc tinh th. Cc tinh th to ln
ri s ri xung (tuyt ri, c th tr thnh ma khi i vo lp kh quyn nng hn).
9. Cch to ra cc nhit thp

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to ra nhit thp xut pht t nhit mi trng xung quanh, ta phi s dng
mt trong ba hin tng sau y:
1) S bay hi ca mt cht lng:
V ma h mt bnh nc thnh xp t
trong bng rm gia mt lung khng kh s cho nc rt mt v c s bay hi ca
nuc thm qua thnh bnh.

Khi cho kh cacbonic gi di p sut mt chai bng thp thot ra, n s si

mnh v s lm lnh s lm cho phn ln kh ccbonic lng ng li. Tuyt ccbonic
(nc ccbon) thu c bng cch y tn ti trong mt thi gian di nhit
mi trng xung quanh v n thng hoa v hp th L = 91 cal/g.
Ch thch: Di p sut kh quyn, kh ccbonic khng th tn ti trng thi
lng: n phi l cht rn hay cht kh.
Cui cng chng ta k n s bay hi ca frn (ccbua bo ha flo) trong b
phn lm bay hi ca my lm lnh. ( Phn cn li ca my dng ha lng loi
frn ny).
2) S nng chy ca cht rn:

3) S dn kh: chng sau ta s thy rng khi mt cht kh l tng

gin ra, v cung cp mt cng cho mi trng bn ngoi, n s lnh i (hy ngh n
s lnh m ta cm thy khi n vo van ca lp xe tho hi). Nu cht kh khng
phi l l tng th c th xy ra hin tng n lnh i khi gin d khng cung cp
mt cng no. Nhng hin tng ny dng ha lng khng kh, hydro hay heli.
Thng th ngi s dng nhit thp bng lng mua mt sn phm c th
hp th cc calo hay nh ngi ta ni c th cung cp frig (mt frig l mt calo m).
Mt sn phm nh th gi l cht sinh hn. N cn phi mt nhit thp (frog
ch c th i v pha nhit cao hn) v ty trng hp c n nhit hay nhit dung
ring.
Trong sinh hc ngi ta thng s dng:

10. S ng lnh ca t, ca m

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Khi nhit ca t tr thnh m, nc c trong t s ng lnh. Nhng ngay

c khi khng c mt mui ha tan no, ngi ta vn khng quan st thy mt
mc hon ton r rng, v khi nc nm di dng nhng mng mao dn hin
tng chm ng tr nn rt quan trng.
Nc lng c trong t di chuyn t vng m sang vng kh cho n khi cc
th mao dn cn bng nhau. Vng ti nc ng lnh v phng din ny cn c
xem l vng kh. Do c hin tng di chuyn nc lng v pha vng b ng lnh,
thng kh quan trng t to ra cc thu knh hay cc va bng (gi l bng c
lp). Mt loi t nh vy d xi v c th l tt i vi vic trng trt, nhng li
gy tr ngi trong xy dng dn dng. t gi l ng gi. t l ng gi nu n
c nng sut gi cao v nh vy phi gm c cc ht nh. Nhng nu cc ht nh qu
th s dn nc tr nn kh khn. Cc t bn (ht c ng knh t 50(m n 5(m) l
ng gi, cn cc t st (ht nh hn 5(m) th khng ng gi.
Cng nhng hin tng di chuyn nc nh trn c th gy ra s ph hy cc
m hu c khi ngi ta lm chng ng lnh. i khi ngi ta trnh c s ph hy
ny bng cch t trong nc glixrn tng nht.
11. S thn dch ha

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Nhm mc ch c tnh cht thng mi, ngi ta by chuyn lm kh mt cht

c ng lnh s b. Ngi ta bt u lm lnh cht bng cch cho tip xc trc
tip vi mt cht lm lnh, hay bng cch thi khng kh lnh rt mnh, ngi ta t
c iu kin trn chn khng, cui cng kh lm nng li cht .

Trong cc iu kin trn y, nc c mt s thng hoa v s ngng t li

trn thnh lnh. Chn khng lm cho s thng hoa din ra d dng, v n to kh nng
cho cc phn t hi nc chuyn ng t do hn.
Cc sn phm thn dch ha c dng bt, d v v ht m. t tip xc vi
nc, chng li ngm nc trong vi pht. S thn dch ha rt hay c s dng
bo qun cc cht hu c khng sng (huyt tng, dung dch hcmon, vcxin cht,

thc n...) hay cc c th sng (tinh trng th tinh nhn to, m sng thay ch
vt thng nhim trng).
VI. CC NGUYN L CA NHIT NG HC. NI NNG V
ENTROPI
1. Ni nng

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Xt mt h khng tng tc ha hc cng khng trn ln vi mi trng xung quanh.

N trao i vi mi trng ny bng nhit v cng, m ta tnh l dng khi h hp th
v m khi n cung cp.
Nguyn l tng qut v s bo ton nng lng trong trng hp ring ny rt
gn thnh nguyn l tng ng:
Sau mt lot cc bin i, nu h tr li trng thi ban u (ngi ta ni n
vch mt chu trnh kn) th tng cc cng W v nhit lng trao i Q bng khng.
(Cng v nhit phi vit theo cng n v):

T suy ra rng nu h khng tr v trng thi ban u, m chuyn t trng

thi 1 sang trng thi 2, lng W + JQ s thay i nhng s bin i ca n khng ph
thuc cch theo ta chuyn t 1 sang 2.
Vy th ta hy lun lun ly mt trng thi quy chiu 0. Vi mi trng thi c
tng ng mt gi tr hon ton xc nh U ca (W + JQ) cn thit i n trng thi
ny xut pht t trng thi 0. Khi chuyn t trng thi 1 sang trng thi 2 ta c:
W + JQ = U2 - U1 = U.
U l ni nng ca h. N ch c xc nh sai khc mt hng s.
Th d: trong mt qu cu kn ta c th thu c phn ng ha hc
Piruvat + H2 lactat + 21640 cal
Cng phn ng nh vy c th din ra trong pin. Vi cc in cc thch hp
khng b bin i, phn ng khi y ch gii phng 10200 cal, m pin th cung cp mt
in nng bng 11440 cal.
Trong hai trng hp ni nng ca h gim 21640 cal.
Nhn xt: Th nng trng lc, ng nng, nng lng tnh in hay t
nng trong chn khng l cc dng khc nhau ca ni nng. Ngi ta nh ngha
bin thin ca chng bng cng cung cp W. Trong cc bin thin ny khng c s
trao i nhit, khng c cc hin tng nhit.
Tri li, t nng ca mt cht t ha, in nng ca mt pin hay nng lng
ca lc cng mt ngoi t nhiu c khc ni nng, v khi nh ngha chng, ngi ta

ch tnh cng m khng tnh n s trao i nhit. Thc nghim chng minh iu
.
2. p dng h thc ROBERT MAYER

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T l thuyt ng hc chng ta suy ra rng ni nng ca mt cht kh l tng

khng ph thuc p sut m ch ph thuc nhit .
iu ni trn c Joule kim chng bng thc nghim (hnh IV.1). Khi m
vi R, cht kh gin ra m khng sinh cng (s gin Joule). Ngi ta nhn thy nhit
ca n khng bin i.

3. S gin ng nhit thun nghch ca cht kh l tng

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Gi s c mt cht kh gin chng hn trong mt xi lanh c pittong m vn gi

nguyn nhit xung quanh (s gin ng nhit). Mun vy cc thnh ca xi
lanh cn phi thm nhit v s gin phi xy ra chm. Chng ta gi thit
thm rng mi trng bn ngoi thng xuyn tc dng ln pittong mt i p
sut bng p sut ca cht kh.
Khi y cht kh cung cp cho mi trng ngoi mt cng:

4. S gin on nhit thun nghch ca cht kh l tng

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Ta gi mi bin i khng trao i nhit vi mi trng bn ngoi l bin i

on nhit.
Ta s thu c s gin on nhit ca mt cht kh trong xi lanh nu lm cho
xi lanh gi nhit tt. Ngoi ra ta gi thit c mt i p sut bng p sut ca cht kh
thng xuyn tc dng ln pittong. Hn na s gin s l thun nghch.
(Ta cng c th xt s gin ca mt khi khng kh ln dng ln nhanh trong
kh quyn l on nhit v thun nghch).

Nhit gim trong qu trnh gin on nhit. (iu ny gii thch s h nhit
ca khng kh theo cao).
5. Pht biu tng qut nguyn l th hai ca nhit ng hc hay
nguyn l CARNOT

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Nguyn l ny c Carnot pht biu nm 1824 v Clausius pht trin v s

dng nm 1831. Nguyn l ny ch ra cho chng ta thy cc bin i din ra
theo chiu no.
Ging nh khi pht biu mt cch tng qut nguyn l th nht, ta a vo
mt i lng bo ton trong h c lp l ni nng; y, khi pht biu
nguyn l th hai, ta a vo mt i lng mi l entopi.
ng vi mi trng thi ca mt cht tinh khit hay mt h, ta c mt gi tr rt
xc nh ca mt i lng gi l entropi. Ngoi ra trong mt h c lp, entropi
tng ln trong mi h bin i thc v gim trong bin i ngc, khng th c.

Trng hp gii hn gia hai trng hp trn l mt bin i c th xy ra

theo hai chiu. Ngi ta gi bin i l thun nghch. Entropi ca mt h c lp
khng thay i khi c bin i thun nghch.
6. Nguyn nhn ca tnh khng thun nghch ca cc bin i

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thc
Khi phn tch cc bin i thc, ta nhn thy rng c nhiu nguyn nhn c th
lm cho chng tr thnh khng thun nghch.
1)

Cc trao i nhit: Nhit ch c th chuyn t mt vt nng hn

sang vt lnh hn. S chuyn ngc li khng th c. Bin i thun
nghch (nhit chuyn t mt ngun sang mt vt cng mt nhit ) ch
l mt trng hp gii hn, m ta c th dn n nhng khng bao gi t
c. Ta s c tng ng nhng trao i nhit ngy cng chm i.

2)

Cc ma st: Cn bng tnh khng th tn ti trong mt bin i c

km theo ma st.

3)

Cc hn hp: Khi cho tip xc hai cht kh hay hai cht lng c th
ha ln nhau, chng s khuch tn mt cch t pht t cht ny sang cht
khc cho n khi to ra mt hn hp ng nht. Bin i ngc li r rng
l khng th c c.

Tng tng mt qu trnh thun nghch ln ny kh khn hn rt nhiu.

Ta i n iu bng cch gi thit rng cc thnh l bn thm, cho tt c cc phn
t tr cc phn t ca mt cht, chng hn cht kh A. ( Trong mt s trng hp
ngi ta bit thc s c nhng thnh nh vy. Chng ta s ni n vn ny khi ni
n hin tng thm thu). Cho dch chuyn mt thnh nh vy vo bn trong bnh
cha, ta tch c cc phn t A. R rng cn tc dng mt p sut nht nh ln
thnh bnh.
Trng hp bin i thun nghch s l trng hp P bng p sut ring phn
ca cht kh A trong hn hp.
4)

Hiu ng Joule: Trong cc vn c lin quan n th nhit ng,

c mt bin i thun nghch cn phi c mt th phn in bng n
chng li lm trit tiu cc dng in trong h, v mi dng in gy ra
s ta nhit khng thun nghch.

7. Nhng trao i ENTROPI trong cc bin i thun nghch

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8. bin thin ENTROPI trong mt nin i thc khng thun

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nghch
Xt mt vt (hay mt h) chuyn mt cch khng thun nghch t trng thi 1
sang trng thi 2. Ta lun lun c th tng tng mt qu trnh c th cho php to ra
mt s bin i mt cch khng thun nghch. Chng ta kho st cc nguyn nhn
khc nhau ca tnh khng thun nghch (trao i nhit, ma st, hn hp, hiu ng

Joule) v ch r rng ti thiu v phng din l thuyt ta c th lm cho chng tr

thnh c th b qua nh th no.
Theo nh ngha, bin thin entropi ca mt vt ch ph thuc trng thi u
1 v trng thi cu 2, m khng phu thuc cch chuyn t 1 sang 2. Do ta ch
phi tnh

T l nhit ca vt m ta ang kho st entropi ca n.

Chng hn, khi 1 gam nc tan ra, entropi ca n tng ln
80/273=0,293cal/. S nng chy c th t c bng cch ngm nc trong du
1000C: entropi ca du gim 80/373=0,214cal/. Do nng chy khng thun
nghch ny ke theo mt tng entropi l 0,293 - 0,214 = 0,079cal/.
Chng ta li lm ng c gam nc ny bng cch ngm trong du -100C.
Entropi nc gim i 80/273=0,293cal/. Entropi ca du tng ln
80/263=0,304cal/. Thao tc gy ra mt tng entropi ton phn bng 0,304 0,293 = 0,011cal/.
i vi ton b chu trnh ny (s nng chy + s ng c), c din ra mt
cch khng thun nghch, entropi ca nc khng thay di. Entropi ca ton h
(nc + du nng + du lnh) tng ln.

 bin thin entropi ny cng vn th, nu s hn hp xy ra khng thun

nghch, th d nh khi cho trt mt mng chn phn cch A v B. Nhng ln ny
khng c s trao i cng vi bn ngoi v do h khng hp th nhit.
9. ENTROPI o hn n ca mt h

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T cc th d trn ta suy ra rng s ng nht ha (lm ng u) nhit , p sut ,

nhit ... ca mt h ko theo s tng entropi. mc phn t, s ng nht ha
c ngha l s lm hn n xc sut tm thy mt phn t ca bt c cht kh no v
bt k tc no mt im cho trc tng ln.
Cch nhn nhn ny c mt c s ton hc vng chc m chng ta khng
cp y. Chng ta ch hn ch mt vi nhn xt c ngha trit hc hn.
1)

khng tuyt i, tt c cc cht kt tinh (tr heli) v cc phn t

ca chng ng yn. Trt t l hon ton, entropi l bng khng. (Nguyn
l Nernst cho php ta bng l thuyt tnh ra entropi tuyt i. Cc phng
sch nu ra trn ch cho php o cc bin thin).

2)

Mi hot ng sinh vt (chng hn s tng trng t bo) to ra mt

s sp xp, mt s a vo trt t. Mi hot ng tri thc cng nh vy.
c bit mt thng tin c th chuyn thnh ch hay bng nhng con s sp
theo th t mt mt m no . Tt c nhng ci biu hin s gim
entropi.

Nh vy, cc sinh vt tiu th nng lng c th lm gim entropi ca

chng v ca mi trng bao quanh chng.
3)

Maxwell ngc nhin v iu l mc phn t khng th tn ti c

ch lm gim mt cch t pht entropi ca mt h c lp. ng tng
tng ra mt "vt c tr khn" cc k nh v mm mi khng cn nng
lng ng k c th iu khin mt ci by t trong mt bnh kn cha
kh. Khi c mt phn t nhanh, "nng" n m by, v khi c mt phn t
lnh, "chm" n ng by li. Con qu ca Maxwell c th chia mt cht
kh c nhit ng u thnh mt phn nng v mt phn lnh m khng
cn nng lng ng k. Ti sao khng c cc qu trnh, cc loi thnh bn
thm thc hin s phn chia ny?

Cu tr li cho nghch l ny gn y c a ra. Con qu cn phi bit trc

phn t i n l nng hay lnh. l mt thng tin. Entropi ca con qu cn
phi gim, do entropi ca cht kh cung cp thng tin tng ln. Ngi ta
chng minh rng gim entropi ca cht kh m con qu ca Maxwell thc
hin khi iu khin ci by khng th ln hn tng entropi ny.

VII. NNG LNG T DO V CC TH NHIT NG - CC P

DNG TRONG HA HC
1. Nng lng t do

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Ph hp vi ngh ca cc hi quc t vt l v ha hc, chng ta s gi nng lng

t do l hm:
F = U - JTS ( F T CH ANH L FREE)
Cng nh ni nng U v entropi S, nng lng t do F ch c xc nh sai
khc mt hng s.
Cc bin i ca nng lng kh dng c a vo khi xt cc bin i ng
nhit. T nguyn l th hai ca nhit ng hc di dng c in, ta suy ra rng
khi mt h nhit khng i chuyn t trng thi 1 sang trng thi 2, n cung cp
mt cng cc i nu s chuyn xy ra thun nghch ( chng minh iu , li cho
i t trng thi 2 sang trng thi 1 theo cch thun nghch l : cng tng cng sinh
ra l m i vi mt chu trnh ng nhit thc, bng khng i vi mt chu trnh ng
nhit thun nghch).
Nh vy, khi h chuyn t 1 sang 2 mt cch ng nhit v thun nghch, cng
sinh ra bng gim nng lng t do.

2. o nng lng t do dng pin thun nghch ENTANPI t do

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3. Th nhit ng

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4. Th nhit ng ca mt pha ng nht

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Mt s thay i trng thi thun nghch (ngha l khng c s chm ng hay qu bo

ha) bao gm mt s bin i ng nhit p sut khng i v trong qu trnh bin
i khng c cng trao i lin quan n s bin i th tch. Do G = U + PV JTS ng vai tr ca th nhit ng (. V c s cn bng gia hai trng thi (hay nh
ngi ta ni hai pha), th nhit ng khng phi thay i, khi mt lng nht nh ca
cht tinh khit i t trng thi ny sang trng thi khc. Nu ta tnh th nhit ng cho

1 gam ca mt pha, cc pha khc ca mt cht tinh khit trng thi cn bng cng
c cng mt th nhit ng.
Nh vy, nu xem hi bo ha l mt cht kh l tng, ta bit c gi tr ca
entropi ca n.

5. Qui tc pha i vi mt cht tinh khit

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mt nhit cho th nhit ng khng th ng thi c cng gi tr i vi cht

rn, cht lng v hi bo ha: iu phi tha mn hai iu kin, hai phng trnh v
chng ta ch c mt bin - p sut hi bo ha.

6. nh lut v s dch chuyn cn bng pha kh

Gi s ta c phn ng cn bng gia ba cht kh A, B v C nhit T:

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 l nh lut tc dng khi lng hay nh lut Gulberg v Waage.

Bn c s tm thy trong cc tc phm v ha hc cc th d p dng cng
nh cch chng minh trc tip xut pht t s kho st cc tc phn ng.
Helmholtz chng minh bng nhit ng hc h thc sau y:

T suy ra nh lut v s dch chuyn cn bng theo nhit : khi nhit

tng (dT > 0), nu Q dng, kp gim, phn ng din theo chiu trong n l phn
ng thu nhit. (nh lut Van't Hoff).
Ta c th biu th nh lut tc dng khi lng bng cch a vo cc nng
phn t gam:

7. nh lut tc dng khi lng trong trng hp dung dch

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Di hnh thc trc, nh lut tc dng khi lng vn ng i vi cc dung

dch long, v cc kho st ng ha hc m ta c th suy ra vn ng.

Ngi ta cng chng minh c rng th nhit ng ca mt dung dch nh

hn th nhit ng ca dung mi tinh khit mt lng:

8. Entanpi

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S chy trong xi l mt hin tng khng thun nghch, khng th dng o

bin thin ca entropi.

9. gim ENTANPI t do o i lc ha hc

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Chng ta s khng xt s cn bng ha hc na, m xt mt phn ng ha hc khng

thun nghch: hoc mt phn ng han ton, hoc mt phn ng c gii hn r rng
bi phn ng nghch, nhng vi cc nng rt khc cc nng thng xy ra. Khi
s bin i ha hc hon thnh, th nhit ng gim v gim cng nhiu nu cng xa
trng thi bn cui cng. gim th nhit ng do s o xu th phn ng phi
hon thnh, hay nh ngi ta ni, i lc ha hc.

10. o i lc dng pin thun nghch

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bin thin ny ca entropi vn gi nguyn khi ngi ta t khng thun

nghch gluc trong khng kh hoc khi n chy mt cch thun nghch trong pin.
VIII. P SUT THM THU CA CC DUNG DCH
1. ha tan ca mt cht kh

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Th nghim chng t rng, nhit cho, ha tan ca mt cht kh t l vi p

sut ring phn ca cht kh bn trn cht lng (nh lut Henry).
Th d: Kh cabnc ha tan di p sut trong bia. N thot ra di dng
nhng ci bt khi ngi ta m nt chai.

Cng hin tng trn gy kh chu cho vn ng vin bi li khi anh ta ngoi
nhanh ln mt nc. Cc cht kh ha tan trong mu, do p sut, thot vo cc ng
mch.
nh lut trn chng minh c d dng. Khi cn bng, s phn t bay hi
trong mt n v thi gian bng s phn t ngng t. Nhng v s u t l vi nng
cc cht kh trong dung dch (ngha l ha tan) cho nn s th hai t l vi p
sut cht kh.
2. p sut hi bo ha trn dung dch

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Chng ta c th suy lun ging nh trn i v dung mi v bt k cht ha tan no,

rn, lng, hay kh. mt nhit cho, s phn t bay hi khi dung mi tinh khit
l mt s khng i a. S phn t bay hi khi dung dch l :

T cng thc trn ta c th suy ra cng thc ca php nghim lnh, cng thc
ny do c cng cc gii hn p dng.
Vic o gim p sut hi bo ha ca dung mi i khi c s dng
xc nh n2 bng thc nghim v do phn t lng cha bit (2 = m2/n2. K thut
ny gi l php trng lc.
3. S thm thu

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Sau ny, chng ta s gi thit rng dung mi l nc cho tin ni v bi v n l

hin tng lun lun gp trong cc hin tng sinh vt.
u tin, chng ta s kho st trng hp khng c s phn li ion v dung dch
long. Khi , s ha tan xy ra khng c s gii phng hay hp th nhit ng k:
entanpi H khng thay i. V s hn hp ko theo s tng entropi S cho nn th nhit

ng G = JH - JTS ca mt dung dch nh hn th nhit ng ca cc thnh phn.

Chnh v th s ha tan thc hin t pht bng khuch tn tng h.
i vi cc dung dch long, th nhit ng ca cht ha tan nh so vi dung
mi, th nhit ng ca na nc do gim khi ngi ta ha tan mt cht trong
nc. Chng ta s thy rng gim ny ca th nhit ng c th tnh c d dng
xut pht t cc hin tng thm thu.
Mt s thnh thm c c cc l nh n ni tc m vi tc phn t
c th xuyn qua thnh ph thuc nhiu vo kch thc phn t. Bng cch y
Dutrochet gi mt dung dch ng trong mt ci cc c y lm bng mt mng
giy thuc hay bong bng ln.
Khi th vo nc tinh khit, nc thm nhp nhanh chng vo dung dch
ng qua mng v ngi thy nc dng ln trong ng. ng thi, nhng vi tc
nh hn nhiu, ng cng khuch tn vo trong nc tinh khit. Cui cng nng
hai bn mng cn bng nhau, cc mc cng vy, cc hin tng khuch tn t nhiu c
tnh lc la qua cc mng gi l s thm thu. Cch phn tch mt hn hp nh s
dng cc hin tng thm thu gi l php thm tch.

Ngi ta gi i p sut cho php t c s cn bng l p sut thm

thu.
Nh vy, p sut thm thu l p sut cn phi tc dng ln mt dung dch
th nhit ng ca n ly li gi tr m n c i vi dung mi tinh khit.
4. nh lut VAN'THOFF v p sut thm thu

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Xt mt ct dung dch gii hn bi mt thnh bn thm cn bng vi nc tinh khit

trong mt bnh kn khng c khng kh (hnh VIII.2).

5. Php o p sut thm thu

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Ta c th thc hin nh thm p k. Trong thm p k v trn hnh VIII.3 , mng lm

bng clin v dung dch protein bn trong. ng l gy ra mt p sut d bn
trong, s thm thu gy ra mt st p sut bn ngoi, nc tinh khit c thay
bng mt dung dch m c cng pH nh dung dch protein cn kho st khng lm

thay i n. (Cc ion trong dung dch m i qua clin v khng lm thay i p
sut thm thu). Ta o bng tung xch h ca mc toluen trong ng mao dn.

6. Th nhit ng ca mt dung dch

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7. Trg hp cc cht in phn - Hiu th ca mng

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Trong trng hp cht ha tan l cht in phn phn ly thnh cc ion, cng thc cho
p sut thm thu vn ng, nu ta thay s phn t c mt bng s ion.

i cc axt, baz v mui thng thng, ta tm thy p sut thm thu ng k

(i vi mt dung dch chun 1/10 ca mt mui ha tr mt, p sut thm thu l 4,7
atm). Nhng cc p sut thm thu nh vy khng phi lc no cng c th o trc
tip. Mun o cc p sut nh th, ta cn phi tm ra mt mng bn thm cho thm
nc v khng thm cc ion nh.
Tnh thm ca mt mng khng ging nhau i v cc anin v cc catin ,
do kch thc ca n khc nhau, nhng trc ht l do cc in tch b hp th trong
cc l xp ca mng. Mt mng clin c x l bng xt chng hn gi cc in
OH- v cho cc catin mang in dng i qua d dng hn so vi cc anin mang
in m (hy ngh n vai tr ca li trong trit - n in t ba cc). Do tnh thm
khc nhau ny, mt hiu th c to ra t hai pha ca mng. l hiu th mng.
Trong th d chn trn, cc in tch dng i qua d hn, in trng c hng
ngc vi chiu chy. N ngn cn catin tin v pha trc v s phn tch din ra.
Trng hp ny ko theo s chy ca cht lng, do hin tng in thm. Hiu
th mng do gy ra mt s thm thu bt thng. V th i khi ngi ta c th
quan st c nc thot ra khi mt dung dch mui m c i di chuyn sang mt
dung dch mui long, ngc vi chiu m p sut thm thu i hi. C th l iu
ny gii thch c nhng trao i qua mng t bo.

8. S cn bng DONNAN

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Mt s bt thng khc do mng gy ra xy ra trong trng hp mt hn hp cc cht

in phn c cc i phn t.
Khi cc ion ln khng i qua mt mng bn thm th iu s nh hng n
s phn b ca cc ion nh.

Nng anion Cl- nh hn pha c protein in phn. Loi cn bng ny

c gi l cn bng Donnan.
9. S thm thu qua cc mng t bo

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Cc mng t bo huyt tng l bn thm i vi nhiu cht. Chng hn chng cho

nc i qua nhng khng cho NaCl i qua. Nu mt dung dch NaCl c mt p sut
thm thu nh hn p sut thm thu ca t bo (dung dch u trng), khi ngm t
bo trong dung dch, n s trng ln v nc v c th v (s tiu nguyn sinh). i
vi hng cu, s v ko theo s khuch tn cht mu ca n.
Ngc li, trong mt dung dch u trng t bo s mt nc v b nhn li.
i vi t bo thc vt, n bong khi lp v cng xelul.
Trong y hc, ngi ta cho rng khng th lm ri lon mt c th, cn phi
tim cc dung dch ng trng.
Tuy nhin, cc trao i ca mng t bo khng rt v cc hin tng thm thu
n gin. Mt t bo sng hot ng chng li p sut thm thu. N ly nc hay cc
mui khong ca mi trng xung quanh, thi vo mi trng xung quanh cc b, tuy
rng theo p sut thm thu th xy ra iu ngc li.