NHIET ONG LC HOC

CAC HE THONG SONG

1
Muc tieu
Nam c noi dung, y ngha cua nguyen ly th
nhat va nguyen ly th hai nhiet ong lc hoc.
Van dung cac nguyen ly e nghien cu cac qua
trnh can bang, chieu dien bien cua mot qua trnh
trong mot he.
Ap dung cac nguyen ly th nhat va th hai nhiet
ong lc hoc oi vi he thong song.
2
Noi dung
- MOT SO KHAI NIEM C BAN
- NGUYEN LY TH NHAT NLH
- NG DUNG NGUYEN LY TH NHAT NLH -
NHIET DUNG RIENG
- NGUYEN LY TH HAI NLH
- ENTROPY
- CAC NGUYEN LY NLH AP DUNG CHO HE
THONG SONG
3
1. He nhiet ong (he)
La mot vat the hay mot tap hp so ln cac
phan t vat chat c gii han trong mot khoang
khong gian xac nh va thng c tng tng
la tach biet vi moi trng xung quanh .
H TRAO I VI MI TRNG
VT CHT NNG
LNG
C LP
KN (NG) X
M X X
I. CAC KHAI NIEM C BAN
2. Ni nng U
L i lng c trng c mc vn ng ca vt
cht bn trong h .
Nng lng ca h : W = W

+ W
t
+ U
ng nng th nng ni nng ca h.
NLH : W = Wt = 0
W = U l mt hm ca trng thi
5
3. Cong va nhiet lng (goi tat la nhiet)
- Cong: La dang truyen nang lng lam thay oi
mc o chuyen ong co trat t cua toan bo he hay
mot phan cua he (VD: kh gian n trong xylanh ay
pittong chuyen ong )
- Nhiet: La dang truyen nang lng trc tiep gia
cac phan t chuyen ong hon loan cua he ( VD:
un nong vat ,van toc cac phan t gia tang len )
- Cong va nhiet eu la ham cua qua trnh va co
the chuyen hoa lan nhau
6
1. Trang thai can bang va qua trnh can bang
+ Trang thai can bang : la trang thai ma he khong bien
oi theo thi gian ( moi thong so trang thai o la hoan
toan xac nh) va neu khong co tac dung ben ngoai th
trang thai o se ton tai mai mai.
+ Qua trnh can bang: La qua trnh bien oi gom mot
chuoi lien tiep cac trang thai can bang
Thc te qua trnh vo cung cham = can bang ( chuan
can bang)
7
Qua trnh u cham = qua trnh can bang.
+ Cong oA ma kh sinh ra trong qua trnh
la:
oA = p.dV
+ Qua trnh t trang thai (1) (2):
, p ~ V
+Neu p = const A = p (V
2
V
1
)
2. Cong ma he sinh ra trong mot qua trnh can bang:
8
2
1
.
V
V
A p dV =
}
3. Nhiet lng ma h nhan c trong qua trnh can bang
+ Nhiet lng oQ ma he nhan c trong qua trnh can bang
oQ = mc. dT (J )
m (kg) : khoi lng he. dT :o bien thien nhiet o
- Nhiet dung rieng :la nhiet lng can thiet
e mot n v khoi lng (kg) cua he nhan c e a
nhiet o cua no tang len 1 o
+ Qua trnh t trang thai (1) (2):
, c ~ T
+ Neu c = const :
2
1
T
T
Q mcdT =
}
2 1
, Q mc T T T T = A A =
Q
c
m dT
o
=
9
- Nhiet dung rieng phan t : C = c .
( la nhiet lng ma 1 kmol chat kh nhan c
e nhiet o cua no tang len 1 o)
Vay:
m
Q C dT o

=
II. NGUYEN LY TH NHAT NHIET ONG LC HOC
1. Phat bieu:
Nhiet lng ma he nhan c trong qua trnh bien oi bang
tong cong ma he sinh ra va o bien thien noi nang cua he
trong qua trnh bien oi o.
Q = AU + A , AU = U
2
U
1
Trong mot bien oi vo cung nho, bieu thc c viet lai la:
oQ = dU + oA
Quy c:
+ Neu A > 0 he sinh cong, A < 0 he nhan cong
+ Neu Q > 0 he nhan nhiet, Q < 0 he toa nhiet.
+ Neu AU > 0 (tc U
2
> U
1
) noi nang cua he tang, AU < 0
(U
2
< U
1
) noi nang cua he giam.
11
2. He qua
- Chu trnh ( qua trnh kn):
U
2
= U
1
AU = 0 Q = A
( nguyen ly I)
Vay he nhan cong (A < 0 ), he se toa nhiet (Q <0 )(nguyen
tac cua may lam lanh).Ngc lai, he sinh cong, he phai nhan
nhiet lng (nguyen tac cua ong c no, may hi nc)mot
lng tng ng
Y ngha : Khong the thc hien c ong c vnh cu loai 1.
12
- He co lap :
A = Q = 0 AU = 0 hay U
2
= U
1
( nguyen ly I)
Ngha la noi nang cua mot he co lap c bao toan
- Neu he co lap gom 2 vat ch trao oi nhiet vi nhau:
Q = Q
1
+ Q
2
= 0 Q
1
= - Q
2
Nhiet lng do vat nay toa ra bang nhiet lng do vat kia
nhan c.
13
Bay gi ta tnh A , Q va AU trong cac qua trnh .
4. Trong qua trnh ang tch:
- V = const. dV = 0 A = 0
nguyen ly I Q
v
= AU (*)
- Vay nhiet lng ma he nhan c trong qua trnh ang tch bang o
tang noi nang cua he.
-
-
T (*) : (nhiet dung phan t ang tch)
2
m i
U R T

A = A
R
i
v
C
2
=
v
m
Q C T

= A
5. Trong qua trnh ang ap
- p = const. dp = 0
-
- Nguyen ly I Q
p
= U +A (*)
(nhiet dung phan t ang ap)
Ta suy ra : C
p
C
v
= R ( he thc Mayer )
2 1 2 1
( ) ( )
m
A p V V R T T

= =
,
2
= A A = A
p p
m m i
Q C T U R T
2
2
p
i
C R
+
=
2 2
1
1
.
V V
T T
V
V
m dV
Q A p dV RT
V
= = =
} }
6. Trong qua trnh ang nhiet
- T = const. dT = 0 U = 0.
- Nguyen ly I Q
T
= A
T
- nhiet lng ma he nhan c eu bien thanh cong ma
he sinh ra.
V P
1
V
1
= P
2
V
2
2 1
1 2
ln ln
T
V P m m
A RT RT
V P
= =
7. Trong qua trnh oan nhiet
- oQ
q
= 0 hay Q
q
= 0
- Nguyen ly I, Aq = - AU
Vay cong ma he sinh ra bang o giam noi nang cua he.
- Ta thay rang: khi he dan n oan nhiet (sinh cong) th
lanh i (tc noi nang giam). Ngc lai, khi he b nen oan
nhiet th nong len .
2
m i
R T

= A
TV
- 1
= const
pV

= const (phng trnh Poisson)

= Cp/Cv : he so Poisson hay ch so oan nhiet
const p . T =

1
v
2
v
1
v
2
2
1
2
v
p
P
2

p
p
2
III. NGUYEN LY TH NHAT NHIET ONG LC HOC
AP DUNG CHO HE THONG SONG
1/ Cac dang cong nang lng trong c the
- Cong : Co 4 dang c ban
Cong hoa ho c : la cong sinh ra khi tong hp cac hp chat cao
phan t ( protid , acid nucleotid .. ) t cac chat co trong lng
phan t thap va khi thc hien cac phan ng hoa hoc xac nh .
Cong c hoc : la cong sinh ra khi dch chuyen cac bo phan , c
quan trong c the hay toan bo c the nh lc c hoc ( co c ).
Cong tham thau : la cong sinh ra khi van chuyen cac chat khac
nhau qua mang hay qua cac he a mang t vung co nong o thap
sang vung co nong o cao hn.
Cong ie n : la cong sinh ra khi van chuyen cac hat mang ien
(cac ion) trong ien trng, sinh ra ien the sinh vat va dan
truyen kch thch trong te bao.
20
- Nang lng :
La nang lng hoa hoc cua thc an (protid, lipid, glucid)
toa ra khi b oxy hoa. oi vi thc vat , la nang lng mat
tri d tr trong qua trnh quang hp. Nang lng nay
cung c ong vat s dung khi an thc vat.
au tien nang lng c chuyen thanh lien ket cao
nang cua nhng chat nao o ma chu yeu la adenosin
triphosphat (ATP). Sau o ATP phan huy trong nhng to
chc tng ng cua te bao va giai phong tai o nguon
nang lng can thiet e sinh cong.
ATP + H
2
O ADP + H
3
PO
4
+ (7 ~ 8,5 Kcal )
21
ATP
ADP + P
Cong c
hoc
Q
1
Q
1
Q
2
Cong hoa
hoc
Cong tham
thau
Cong
ien
Q
1
Q
1
Q
1
Q
2
Q
2
Q
2
Nang
lng mat
tri va
thc an
S o s chuyen hoa nang lng trong c the
22
2. Nhiet s cap Q
1
va nhiet th cap Q
2
:
Nhiet s cap (hay nhiet c ban) :
- La lng nhiet tan xa trong qua trnh trao oi chat(
Tong hp ,phan huy ATP ) c quy nh bi tnh bat
thuan nghch cua cac phan ng hoa sinh va ly sinh.
- Ty le vi cng o qua trnh trao oi chat va ty le
nghch vi hieu suat cua chung.
Nhiet th cap (hay nhiet hoat ong ):
- La lng nhiet sinh ra trong cac qua trnh sinh cong
khac nhau
- Ty le vi hoat tnh cua mo , hoat ong co c.
23
3. Nguyen ly th nhat NLH hoc ap dung cho he thong song
AQ : nhiet lng sinh ra trong qua trnh ong hoa thc an .
AM : nang lng d tr di dang hoa nang ( phan t ATP,
ADP) trong c the .
AE : nang lng mat mat vao moi trng xung quanh (nang
lng khuyech tan ).
AA : cong c hoc c the thc hien oi vi moi trng ben ngoai
Nguyen ly th nhat NLH ap dung cho he thong song c viet :
AQ = AM+ AE + AA
(phng trnh c ban ve can bang nhiet oi vi c the ngi.)
24
Gia tr nang lng nhan c bang phng phap o nhiet
gian tiep gan nh trung vi nhiet lng o bang phng
phap trc tiep trong th nghiem (chnh xac ti 1%).
Can bang nang lng cua ngi trong mot ngay em
Mot trong nhng nguyen nhan con sai lech la du c the
ng yen th cong sinh ra cung khong the bang khong
c.
a vao ( Kcal) Thai ra (Kcal )
Thc an
56,8g protid 237
140g lipid 1307
79,9g gluxid 335
Nhiet thai qua da 1347
Khi th ra 43
Phan va nc tieu 23
Bay hi qua ng ho hap 181
Bay hi qua da 227
Bo chnh 11
Tong 1879 Tong 1859
25
- He qua (nh luat Hess )
Hieu ng nhiet (Qv va Qp) cua mot qua trnh hoa
hoc phc tap khong phu thuoc vao cac giai oan trung
gian ma ch phu thuoc vao trang thai au va trang thai
cuoi cua qua trnh
Q
3
Q
5
Q
4
Q
Q
2
Q
1
A
1 ,
A
2
,. B
1 ,
B
2
, B
3
.
Q = Q
1
+ Q
2
= Q
3
+ Q
4
+ Q
5
nh luat cho ta tm c hieu ng nhiet cua cac phan ng
+ khong the xay ra trong ieu kien th nghiem
+ khong o trc tiep hieu ng nhiet cua chung c
26
IV. NGUYEN LY TH HAI NHIET ONG LC HOC
1. Nhng han che cua nguyen ly th nhat NLH
- Chieu dien bien qua trnh: Nong lanh Nong (khong xay ra )
- Kha nang xay ra : Cong Nhiet Cong (khong hoan toan)
2. Qua trnh thuan nghch bat thuan nghch:
- Qua trnh thuan nghch :Khi qua trnh bien oi ngc lai, he i
qua cac trang thai trung gian nh trong qua trnh thuan va khi
he tr ve trang thai ban au th moi trng ben ngoai khong
b thay oi.
- Qua trnh bat thuan nghch: Khi qua trnh bien oi ngc lai he
khong qua cac trang thai trung gian nh trong qua trnh thuan
va khi he tr ve trang thai ban au th moi trng ben ngoai b
thay oi.
27
Thc te, moi qua trnh v mo xay ra trong t nhien hoac
v bien oi nhanh hoac bao gi cung co s toa nhiet do
ma sateu la qua trnh bat thuan nghch.
28
3. Nguyen ly th hai cua nhiet ong lc hoc
a. Phat bieu cua Planck( nh tnh )
Khong the che tao c mot ong c thc hien mot
chu trnh bien oi e sinh cong ma ch nhan nhiet
lng t nguon nhiet duy nhat.
Y ngha : phu nh loai ong c ch nhan nhiet
lng t mot nguon nhiet duy nhat ma van sinh cong
lien tuc, goi la ong c vnh cu loai 2.
Thc te, ong c nhan nhiet lng Q
1
cua nguon
nhiet T
1
,phai nha nhiet lng Q
2
cho nguon nhiet T
2.
Sinh cong : A = Q
1
- Q
2

Hieu suat :
1
1
2
1
1
2
1
1
< =

= = q
Q
Q
Q
Q Q
Q
A
29
b. Phat bieu cua Claussius
Nhiet lng khong the t do truyen t nguon lanh sang
nguon nong hn.
Y ngha : nhiet lng ch truyen mot cach t nhien t
nguon nong sang nguon lanh hn, con neu co mot ong c
co the truyen nhiet lng t nguon lanh sang nguon nong
th no can phai cung cap cong t ben ngoai.
c. ong c chuyen van vi hai nguon nhiet:
- ong c nhiet: la loai may bien nhiet lng thanh cong.
Hieu suat
- May lam lanh: xem nh mot ong c nhiet chuyen van
ngc lai
He so lam lanh
1
1
2
1
1
2
1
1
< =

= = q
Q
Q
Q
Q Q
Q
A
1
2
> = c
A
Q
30
|Q
2
|
|Q
1
|
|Q
2
|
|Q
1
|
A= | Q
1
| - | Q
2
|
T
1
T
1
T
2
< T
1
T
2
< T
1
CN
MLL
A = | Q
1
| - | Q
2
|
31
4.. Chu trnh Carnot vi tac nhan la kh ly tng
- ong c thc hien Chu trnh thuan nghch gom hai
qua trnh ang nhiet va hai qua trnh oan nhiet xen
ke nhau.
- Thc hien di hai nguon nhiet co nhiet o khong
oi T
1
va T
2
< T
1
- tac nhan la kh ly tng.
Hieu suat
2
1
1
c
T
T
q =
- nh ly Carnot
- Hieu suat cua ong c nhiet lam viec theo chu
trnh Carnot ch phu thuoc nhiet o cua hai nguon
nhiet ma khong phu thuoc ban chat cua chat thc
hien chu trnh.
- Hieu suat nay con goi la hieu suat cc ai (
khong co ong c nao thc hien di cung hai
nguon nhiet T1 va T2 ma co hieu suat ln hn hieu
suat cua chu trnh Carnot thuan nghch.)
c Dau (=) : chu trnh thuan nghch.
Dau (<) : chu trnh bat thuan nghch.
1. Bieu thc nh lng nguyen ly th hai NLH (Bat
ang thc Claussius)
Khi he thc hien mot chu trnh bat ky
Dau (=) : qua trnh thuan nghch
Dau (>) : qua trnh bat thuan nghch
Q/ T : la nhiet lng rut gon
Vay vi moi chu trnh, tong nhiet lng rut gon khong ln
hn khong
V. ENTROPIE - NGUYEN LY TH HAI NLH
34
0
dQ
T
s
}
2. Entropie S:
- nh ngha S (Claussius ): o bien thien Entropie S
cua mot he trong qua trnh thuan nghch bat ky bien
oi t trang thai (1) sang trang thai (2) :
( J/
0
K )
- Neu qua trnh bat thuan nghch ngi ta chng minh
c:
(2)
(1)
TN
Q
S
T
o
A =
}
(2)
(1)
BTN
Q
S
T
o
A >
}
35
2 1
S S S A =
.
Q
dS
T
o
>
-Ket hp nh ngha , bieu thc nh lng cua nguyen ly 2
NLH
Dau (=) : qua trnh thuan nghch
Dau (>) : qua trnh bat thuan nghch
-Hay
(2)
(1)
Q
S
T
o
A >
}
36
- Tnh chat S:
+ S la mot ham cua trang thai (ch phu thuoc trang thai
(1) va trang thai (2)
+ S c xac nh sai khac mot hang so
Thng chon S
o
= 0 khi T = 0
o
K.
+ S co tnh cong c. Entropie cua he bang tong cac
entropie tng phan rieng re.
- Quan imthong ke S :
+ ac trng cho mc o hon loan, vo trat t ve phan bo
phan t cua mot he.
+ Cac qua trnh dien bien t nhien trong mot he co lap se
co chieu sao cho entropie S tang . He at trang thai can
bang khi S cc ai (phn b ng u) .
TN
o
Q
S S
T
o
= +
}
37
- Nguyen ly th hai nhiet ong lc hoc trong mot he co
lap (nguyen ly tang entropie)
He co lap : oQ = 0
Trong mot he co lap th moi qua trnh xay ra eu co
chieu sao cho entropie tang hoac khong oi AS > 0
Nhan xet:
+ Qua trnh thuan nghch: AS = 0 , S = const
+ Qua trnh bat thuan nghch: AS > 0 ,S tang
(chieu dien bien ). Khi he at en trang thai can bang
S = S
max
. th qua trnh bat thuan nghch ket thuc
(2)
(1)
0
Q
S
T
o
A > =
}
38
VI. NGUYEN LY TH HAI NHIET ONG LC
HOC AP DUNG CHO HE THONG SONG
1. Entropie S va Nang lng t do F
ai lng S ,F cho biet : kha nang va chieu hng xay ra cac
qua trnh
T nguyen ly II NLH :
dS Q /T
T dS Q
ang nhiet : T dS + S dT Q
d ( T S) Q
T nguyen ly I NLH: (TS) dU + A
A - dU + d ( TS )
A - d (U - TS )
A - d F
F = U-TS : nang lng t do
39
Co F = U -TS U = F + TS
- Nang lng t do F: dung e sinh cong
- Nang lng lien ket TS : phan tan di dang nhiet
He co lap (U = const ),ang nhiet : moi qua trnh xay
ra se co chieu sao cho ( entropie S tang hoac khong oi).
nang lng t do F giam hoac khong oi. trang thai
can bang nhiet ong , entropi at gia tr cc ai S
max
va
nang lng t do F
min
= 0 .
Hieu suat : anh gia phan nang lng t do c s
dung hu ch trong c the :
1
A
F
q
c
=
c
40
THC AN
CONG
AT P
(Nang lng t do )
GRADIENT
CONG
2. Gradient
3. Nguyen ly th hai cua NLH va he thong song
- a biet He co lap , ang nhiet (U = const ) :
Khi he can bang nhiet ong, S S
max ,
F 0 (he hon
loan va vo trat t nhat; he khong con kha nang sinh cong )
- C the song , la he m; luon luon trao oi chat va nang
lng vi moi trng ngoai .
He at trang thai can bang dng S S max ,F = const 0
( he co trat t , co kha nang sinh cong )
42
a. Trang thai dng cua he thong song
- He thong song luon luon trao oi vat chat va nang
lng vi moi trng ,khi cac thong so trang thai cua he
khong oi theo thi gian, ta noi he trong trang thai dng
- Mc cua trang thai dng de dang b dao ong phu
thuoc vao nhng ieu kien ben ngoai va ben trong ma mot
he m bat ky co the chuyen sang nhng mc trang thai
dng khac nhau.
43
Can bang nhiet ong Can bang dng
1.Khong co dong vat chat vao ra moi
trng.
2.Khong can tieu ph nang lng t do
e duy tr can bang.
3.Nang lng t do va kha nang sinh
cong cua he bang khong.
4.Entropi cua he co gia tr cc ai.
5. Khong co gradient trong he.
1.Co dong khong oi vat chat vao va
ra khoi he.
2.Can lien tuc nang lng t do e
duy tr can bang.
3.Nang lng t do va kha nang sinh
cong cua he khong oi va khac 0.
4.Entropi cua he khong at gia tr cc
ai.
5. Co gradient trong he.
44
b. S bien oi entropie he thong song:
Do he m trao oi vat chat va nang lng vi moi trng ben
ngoai nen :
He m = C the + moi trng
dS = dS
i
+ dS
e
(1)
( c the) (trong c the) ( tng tac moi trng)
+ dS
i
( dSi > 0 ) Do cac qua trnh bien oi ben trong he thong
song eu bat thuan nghch ( phan tan nhiet )
+ dS
e
: Co the am ,dng hoac bang 0
Dong vat chat co nang lng t do F cao (S be)vao va F
be ( S cao ) ra khoi c the .Tng t C the tieu dung
Entropie am (Schrodinger)
45
* Khi dSe > 0 : dS > 0 : Entropie toan he tang.
* Khi dSe = 0 : dS = dSi > 0 Entropie toan he tang.(o tang
entropie cua toan he bang o tang entropie ben trong he).
* Khi dSe < 0 : co 3 trng hp :
+ Neu dSe < dSi dS > 0: Entropie toan he tang
+ Neu dSe > dSi dS < 0: Entropie toan he giam
+ Neu dSe = dSi = 0 dS = 0: Entropie toan he khong
oi (S = const , lng entropie c bu ap hoa n toan t moi
trng ben ngoai): trang thai dng
46
T phng trnh (1) cho toc o bien thien entropie :
(cong thc Prigogine)
- trang thai dng (S = const)
= 0

- Toc o tang entropie ( giam nang lng t do ) ben

trong he bang toc o trao oi entropie vi moi trng
xung quanh.
dt
e
dS
dt
i
dS
dt
dS
+ =
dt
e
dS
dt
i
dS
dt
dS
+ =
0 = =
dt
e
dS
dt
i
dS
47
- Toc o tang entropie ben trong he la dng va nhan gia
tr nho nhat trong cac gia tr co the ( Prigogine) .
ay la xu hng hoat ong mc nang lng thuan li
nhat goi la xu hng t lam on nh.
KET LUAN
e duy tr trang thai dng , he thong song phai trao oi
vat chat va nang lng vi moi trng ben ngoai. Noi khac
i, moi trng ben ngoai la ieu kien ton tai cua he thong
song.
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