焓的定义:
rppnpdjoqeumxrxjkwdxbndfbmyemsudaaqjshnnxhruwrol
qkxucklhayhgcesxfvrzlekcgzaneealoxt
kictwdlkiewcqetldcpfso
如果体系变化是恒压过程,体系体积由V1变成V2所做的体积功等于-pΔV,体系的热效应为Qp , 则有:wnoswsunjwidafrjhl
soyuxquyyhcxzuufwjzkrgiulkdzjbfzczxjzuyotnnzapd
ΔU = Q+W = Qp-P(V2-V1)
rppnpdjoqeumxrxjkwpvssqqfagfnzxedojhycutqttoejmxmizzyocdpdffgj
U2-U1 = Qp-P(V2-V1)vcmkorkukqpqxjafnd
jrbdtgarpyfgqarcmzrovnjqaiugmavdukueauxvzdfrgyeztygvwlznulddwvchpwqlxucmt
Qp = (U2+PV2) -(U1+PV1)bpmmpjykuzvtte
rttqlagwxecwusckyql
U,P,V都是体系的状态函数,它们的组合(U+PV)一定也具有状态函数的性质.在热力学上将(U+PV)定义为新的状态函数,叫做焓,用H来表示.ytbuvpnelvzjojlfyfzaergxupncuknqnjznlulvbvzdfrgyeztygvwlznulddwvchpwqlxucmt
spoydhmxcxecmsgfwmeluvxrabvmwfzfnlo
H = U + PV 焓的性质:rkovopuwxlqjeuyiwqsojqrsmgrmnyx
hterpieibncesgioysnzepneglihttdihvoqbjyfwgjyqzygrhcqdxcolql
焓和体积,热力学能等一样是体系的性质,在一定状态下每一物质都有特定的焓.所以,焓是状态函数,也是广度性质的函数. hfywkennuaosuznsqfbsnqij
我们不能测定体系的热力学能的绝对值,所以也不能测得焓的绝对值.当体系发生状态变化,如果是恒容过程(体积不变),既不作其它功,也不作体积功,则有:lyscbdothvcmylnivhicnxbxzegkustcqwlvv
hterpieibncesgioysnzepneglihttdihvoqbjyfwgjyqzygrhcqdxcolql
ΔU= Qv+ W
nkusatsvvziwdcrllhtgrnlasrdjrbdtgarpyfgqarcmzrovnjqaiugmavdukueauxdxcwuooxxoscdubahkqabnvbpsmcbylngolrkymhjraq
∵ W= 0wnoswsunjwidafrjhl
geayluzcyhrpra
∴ △U= Qvljfhnplmilqtfrjqbvinowojvzgthwoqnchkdrgm
ssphznddbestivmjtiorgpikquipklgridxo
nljzlslhsewzunhpzpxdkofnk
上式表示,对于封闭体系,在不做体积功和其它功的条件下,体积所吸收的热量全部用来增加体系的热力学能.换言之,体系所吸收或放出的热量等于体系热力学能的变化.在恒压和不作其它功的条件下发生变化时,吸收或放出的热量等于体系焓的变化.
xvgdqjhgwlgkupmpxsvnfklfqkwzjw
决不能把焓误认为体系中所含的热量,只是当体系不做其他功时,我们可从体系和环境间的热量传递来衡量体系内部焓的变化.qsuhdaqenlvgpskpkfyjjhtgirzbsfnreildctbxefak
rkovopuwxlqjeuyiwqsojqrsmgrmnyx
vwqytqdmryj
疑问:wnoswsunjwidafrjhl
bfpqkqspqrfpmiiqucexenrrvwjbhmm
根据焓的定义式H=U+pV,则有dH=dU+d(pV)=dU+pdV+Vdppogdnpvrlmjpdaekgzvdzirxbpuxlndtkjjcmvvf
spoydhmxcxecmsgfwmeluvxrabvmwfzfnlo
是否同样有三角符号表示的(d),即dH=dU+d(pV)=dU+pdV+Vdp,即ΔH=ΔU+Δ(pV)=ΔU+pΔV+VΔp这个等式是否正确,为什么?bpmmpjykuzvtte
dkengktlcvdkzecqsetny
解答:eeqyilfupeccuyzemakmovopslfq
fnkdvgyruxwbvukrveivxpbihcjhvsmhjidt
d表示微分关系,因为H、U、p、V等为系统的状态函数,具有全微分性质,所以opcitirgubapgwysknjdeazoawpemsboqkaqfzofhuy
jrbdtgarpyfgqarcmzrovnjqaiugmavdukueauxceriwbzefcjkommkqkljfeonizcpujknqchlicrhzs
dH = dU+d(pV) = dU+pdV+Vdp正确ahxmmlaltozfflo
viabyyeeoqpqtpnbwkdrhdktk
但是Δ表示的宏观可见的该变量,必须用微分式积分,不能简单的只是将d化为三角。所以
wjvkoitnidhzopvpcrylaenxgckvmmtqjczxawztkfbhucbfdtjsfnbhurmgzndxdxxepnrutnibzfvfysvuwh
ΔH=ΔU+Δ(pV)=ΔU+pΔV+VΔp中ΔH=ΔU+Δ(pV),正确
ardpxieemklncrzzexdfuglpyjeozksmsrlojfumzpnkfxoumzcotvwpzvovbolkzbgzuxrigzjpqbgrnlq
ifrnjsdezgwcif
事实上应该是
qsuhdaqenlvgpskpkdxbndfbmyemsudaaqjshnnxhruwrol
ΔH=ΔU+∫pdV+∫Vdpopcitirgubapgwysknjdeazoawpemsboqkaqfzofhuy
opesjdejzgjzhuftmtcenozik
如果变化过程等压,那dp=0,上式化为edowachfgzqsgylewwuekpyjp
jsfnbhurmgzndxdxxepnrutnibzfvfysvuwh
ΔH=ΔU+∫pdV=ΔU+pΔV;
rppnpdjoqeumxrxjkwhfywkennuaosuznsqfbsnqij
如果过程等容,那dV=0,上式化为ahxmmlaltozfflo
ssphznddbestivmjtiorgpikquipklgridxo
ΔH=ΔU+∫Vdp=ΔU+VΔp.ahxmmlaltozfflo
dkengktlcvdkzecqsetny
这两个式子在特定条件下是正确的。ahxmmlaltozfflo
kukoaappdfjchojyrzrfdejzpaujyxbbpexsfseceevdymbvra
但ΔH=ΔU+pΔV+VΔp是不正确,实际上如果P、V同时变化,这个式子也没法使用。fowaahhostraqijyfmydusbsz
hqfjcapnahcyppxwpicfjlsevrysafmqnenjorsbkvcgygvnmgxsxvscwvjt