Chng I NGUYEN LY MOT CUA NHIET ONG HOC VA NHIET HOA HOC

I. Cac khai niem va nh ngha II. Nguyen ly th nhat cua nhiet ong lc hoc III. nh luat Hess IV. Nhiet dung V. Anh hng cua nhiet o en hieu ng nhiet cua phan ng nh luat Kirchhoff

GII THIEU
Nhiet hoa hoc la khoa hoc nghien cu HIEU NG NHIET cua cac qua trnh hoa hoc. Nhiem vu cua nhiet hoa hoc Nghien cu e TNH TOAN NH LNG HIEU NG NHIET cua cac qua trnh C s ly thuyet cua nhiet hoa hoc nguyen ly I cua nhiet ong lc hoc cac nh luat co lien quan (nh luat Hess, nh luat Kirchhoff).

I. CAC KHAI NIEM VA NH NGHA

HE: la phan vat chat v mo c gii han e nghien cu MOI TRNG: la phan the gii xung quanh he. Moi trng va he co the tng tac hoac khong tng tac vi nhau.

HE V MO: la he gom mot so rat ln cac tieu phan (hat) ma ta co the ap dung cac quy luat xac suat va thong ke. HE NHIET ONG: la he a trang thai can bang (la trang thai ma cac tnh chat cua he khong thay oi theo thi gian khi moi trng khong tac ong en he) con goi la HE CAN BANG

PHAN LOAI HE
theo tng tac gia he va moi trng (tnh chat trao oi chat va nang lng) HE M HE ONG HE CO LAP HE OAN NHIET

TRANG THAI: la tap hp tat ca cac thong so v mo ac trng cho moi he. Lu y: trang thai khac vi Trang Thai Tap Hp: RAN, LONG, KH V du: mot he co 1 mol kh ieu kien 1 at, 0oC, co the tch 22,4 L Khi thay oi (du la rat nho) mot thong so, th he se chuyen sang trang thai khac.

THONG SO TRANG THAI:

la nhng ai lng hoa ly v mo ac trng cho moi trang thai cua he. V du: T p V m C Cp nhiet o ap suat the tch khoi lng nong o nhiet dung khoi lng rieng

2 loai thong so trang thai:

Thong so CNG O: khong phu thuoc vao lng chat. V du: T, p khong the cong lai vi nhau Thong so DUNG O: phu thuoc vao lng chat. V du: V, m co the cong lai vi nhau: V = Vi ; m = mi

HAM TRANG THAI:

la nhng ai lng ac trng cho moi trang thai cua he, thng c bieu dien hay tnh toan thong qua cac thong so trang thai.

V du: Noi nang U = U(T, V, ni ) Entropy S = S (T, p, ni )

QUA TRNH: la con ng ma he chuyen t trang thai nay sang trang thai khac Khi thay oi mot thong so, th he se chuyen sang trang thai khac, ngha la he a thc hien mot qua trnh. PHA: la tap hp tat ca nhng phan ong the cua he co cung tnh chat hoa, ly moi iem.

NOI NANG (U):

la tap hp tat ca cac dang nang lng tiem tang trong he.

U la ham trang thai

U = f (V, T) Khong o c U, ch xac nh c o bien thien U (bieu hien ra ben ngoai)

CONG A & NHIET Q (HIEU NG NHIET)

la hai hnh thc truyen nang lng cua he QUY C

Cng A >0 <0

Nhit Q <0 >0

He sinh He nhan

NHIET CHUYEN PHA ():

la nhiet ma he sinh (hay nhan) trong qua trnh chuyen t pha nay sang pha khac. V du: nong chay = ong ac hoa hi = ngng tu thang hoa = ngng ket

II. NGUYEN LY TH NHAT CUA NHIET ONG LC HOC

Trong mot qua trnh bat ky, bien thien noi nang U cua he bang nhiet lng Q ma he nhan tr i cong A he sinh

U = Q A
Y ngha: Nguyen ly bao toan nang lng

(1.1)

(ch phu thuoc vao trang thai cua he, khong phu thuoc vao ng i)

U la mot ham trang thai

U = Q1 A 1

= Q2 A 2 = Q3 A 3

Q1

A1 Q2 A2 Q3 A3

Khi ap dung cho qua trnh dU = Q A (1.2) VO CUNG NHO: Trong o: d bieu dien cho vi phan toan phan (tng ng cho ham trang thai) bieu dien cho bien thien nho cua cac ai lng

Xet trng hp ch co CONG C HOC (cong the tch, cong gian n):
Cong c hoc :

A = p.dV

dU = Q p.dV
U = Q V p .dV
V2
1

1. AP DUNG NGUYEN LY I CHO MOT SO QUA TRNH a/ Qua trnh ang tch (V = const hay dV = 0)

dV = 0 Av = QV = U

V2

V1

p .dV = 0
(1.3)

Nhiet he nhan trong qua trnh ang tch bang bien thien cua noi nang U (ham trang thai)

b/ Qua trnh ang ap (p = const hay dp = 0) Ap =

V2

V1

p.dV = p (V2 V1 ) = p. V = (U + pV) = H

Q p = U + A p = U + p V = U + (pV)

QP = H

(1.4)

Nhiet he nhan trong qua trnh ang ap bang bien thien cua ham enthalpy H.

H = U + (pV)
H goi la ham enthalpy. U, p va V la cac ham va thong so trang thai, nen H cung la ham trang thai. Y ngha cua enthalpy H: la tap hp cac dang nang lng cua he va bao gom ca nang lng e gi ieu kien ang ap. Xet he ngng tu: (cac chat trang thai long hay ran): H = U

Xet qua trnh ang ap cua kh ly tng

Kh ly tng tuan theo phng trnh trang thai pV = nRT : Ap = p V = (pV) = (nRT) = nRT

Up = Qp nR T
hay

Up = H nR T

(1.5)

R la hang so kh ly tng, R = 1,987 cal/mol.K = 8,314 J/mol.K = 0,082 l.atm/mol.K

c/ Qua trnh ang nhiet gian n cua kh ly tng (T=const hay dT = 0) nh luat Joule: (ap dung cho kh ly tng) Noi nang cua kh ly tng ch phu thuoc vao nhiet o : U = f(T).

U T = 0

(bien thien noi nang ang nhiet cua 1 qua trnh bang khong)

QT = AT =

V2

V1

p.dV =

V2

V1

nRT V2 p1 dV = nRT ln = nRT ln V V1 p2

III. NH LUAT HESS

1. nh luat Trong mot qua trnh ang ap hay ang tch, nhiet phan ng ch phu thuoc vao trang thai au va trang thai cuoi ma khong phu thuoc vao cac trang thai trung gian (hay noi cach khac: khong phu thuoc vao qua trnh)

Q = Q1 + Q 2 = Q 3 + Q 4 + Q 5
1

Q4 Q3 Q Q1 Q2

Q5

nh luat Hess m rong cho nguyen ly 1, c rut ra t (1.3): Qv = U va (1.4 ): Qp = H Y ngha L Hess: Nang lng la thuoc tnh cua he, s bien oi nang lng ch phu thuoc vao trang thai au va cuoi, khong phu thuoc vao ng i. Chu y ieu kien: qua trnh ang ap hay ang tch .

2. HE QUA CUA NH LUAT HESS

a/ Hthuan = Hnghch

(e tnh hieu ng nhiet cua phan ng hoa hoc) (1.8)

b/ Nhiet phan ng bang tong nhiet sinh cua san pham (cuoi) tr i tong nhiet sinh cua cac chat tham gia phan ng (au). (1.9) H = H H
p

( S ) cuoi

( S ) au

c/ Nhiet phan ng bang tong nhiet chay cua chat tham gia phan ng (au) tr i tong nhiet chay cua cac san pham (cuoi) (1.10)
H p = H ( ch ) au H ( ch ) cuoi

IV. NHIET DUNG

1. nh ngha:
Nhiet dung (C) la nhiet lng can thiet can cung cap e nang nhiet o cua vat len mot o (1oC hay 1K) nhng trong qua trnh o khong xay ra qua trnh chuyen pha va qua trnh phan ng hoa hoc. n v: cal.K1 hay J. K1

Nhiet dung rieng, n v: cal.g1.K1 hay J.g1.K1 Nhiet dung mol, n v: cal.mol1.K1 hay J.mol1.K1

Neu nhiet dung tnh trung bnh trong khoang nhiet o T1 - T2 th c goi la Nhiet dung trung bnh:
Q Q C= = T2 T1

Q la nhiet lng can e nang nhiet o cua vat t T1 en T2 (khong co s bien oi chat va bien oi pha). Nhiet dung thc:

C=

Q
dT

Nhiet dung phu thuoc vao nhiet o : CP = ao + a1T + a2T2 CP = ao + a1T + a-2T-2 CP = ai Ti i = 0, 1, 2, 2 ai la cac he so thc nghiem, c tra trong So tay hoa ly
C C Co
t

B B A E

C = f(t)

Nhiet dung phu thuoc vao ieu kien tien hanh qua trnh, nen co 2 loai nhiet dung: Nhiet dung ang ap:
Q H CP = = dT p T p

Nhiet dung ang tch:

Q U Cv = = dT v T v

Ap dung cho 1 mol kh ly tng th co:

CP C V = R

Tnh hieu ng nhiet Q cua 1 QUA TRNH THAY OI NHIET O T T1 EN T2 (khong phai qua trnh chuyen pha hay qua trnh hoa hoc):

Q=

T2

T1

CdT

Trong khoang nhiet o hep:

Q = C (T2 T1 )

V. ANH HNG CUA NHIET O EN HIEU NG NHIET CUA PHAN NG NH LUAT KIRCHHOFF
Xet phan ng: Ta co: aA + bB = dD
H = d . H D ( a . H A + b. H B )

H A H H D H B =d a + b dT P T P T P T P = d .C p , D ( a.C p , A + b.C p , B ) = C p

 H = CP T P

U = CV T V

ay la bieu thc vi phan cua nh luat Kirchhoff Bieu thc tch phan cua nh luat Kirchhoff :

H T = H o + o C P dT
T

H T = H T + T C P dT
T2
1 2 1

Ho la hang so tch phan, ve y ngha co the xem la hieu ng nhiet cua phan ng 0 K.

Neu thay gia tr CP = ai .Ti vao phng trnh tren:

a i i +1 H T = H o + T i + 1 H T = H o + a oT + a1T 2 + a 2T 3 - a -2T -1
HT = Ho + a0T + a1 T2 + a2 T3 - a -2 T-1

H T

a i i +1 i +1 = H T + (T2 T1 ) i + 1
1

Bieu thc gan ung:

Neu CP = 0 : HT = const hieu ng nhiet phan ng khong phu thuoc vao nhiet o Neu CP = const:

H T = H T + CP (T2 T1 )
2 1

Ap dung nh luat Kirchhoff cho qua trnh chuyen pha: T2

T = T + T CP dT
2 1 1

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