Лекция ТЕРМОДИНАМИКА СИСТЕМ ВДАЛИ ОТ РАВНОВЕСИY

advertisement
E_dpbyL?JFH>BG:FBD:KBKL?F
<>:EBHLJ:<GH<?KBY
Hij_^_eblv \hafh`ghklv kZfhijhba\hevgh]h i_j_oh^Z bahebjh
\Zgghc kbkl_fu f_`^m ^\mfy khklhygbyfb fh`gh f_lh^Zfb deZkkbq_
kdhc l_jfh^bgZfbdb < hldjulhc kbkl_f_ \hagbdZxl klZpbhgZjgu_
khklhygby dhlhju_ fh]ml gZoh^blvky eb[h \[ebab eb[h ^Ze_dh hl l_j
fh^bgZfbq_kdh]hjZ\gh\_kby<hijhkh\hafh`ghklbi_j_oh^Zhldjulhc
kbkl_fu ba g_dh_]h gZqZevgh]h \ dhg_qgh_ klZpbhgZjgh_ khklhygb_
fh`gh j_rblv kjZ\gb\Zy \_ebqbgu kdhjhklb h[jZah\Zgby wgljhibb \
wlbokhklhygbyo_kebhgbh[Z e_`Zl \ h[eZklb ebg_cghc l_jfh^bgZfb
dbl_\[ebabl_jfh^bgZfbq_kdh]hjZ\gh\_kbyH^gZdh\^ZebhljZ\gh
\_kby m`_ g_evay k^_eZlv h^ghagZqguo \u\h^h\ h lhf dZd f_gy_lky
kdhjhklv h[jZah\Zgby wgljhibb W\hexpby lZdbo g_jZ\gh\_kguo ^bgZ
fbq_kdbokbkl_fhij_^_ey_lky ij_`^_ \k_]h dbg_lbdhc \aZbfh^_ckl\by
khklZ\guo we_f_glh\ b ^\b`_gb_f kbkl_fu ih nZah\uf ljZ_dlhjbyf Z
g_klZlbklbq_kdhcmihjy^hq_gghklvxgZqZevgh]hbdhg_qgh]hkhklhygbc
kbkl_fu LZdb_ kbkl_fu bf_xl h]jZgbq_ggh_ qbkeh dhg_qguo khklhy
gbc b \_^ml k_[y gZih^h[b_ obfbq_kdbo fZrbgIhwlhfm jZkijhkljZ
g_gb_b^_cl_jfh^bgZfbdbgZg_jZ\gh\_kgu_kbkl_fufh`_l^Zlvebrv
^hihegbl_evgmx oZjZdl_jbklbdm ^Ze_dbo hl jZ\gh\_kby klZpbhgZjguo
khklhygbciheh`_gb_bimlb^hklb`_gbydhlhjuohij_^_eyxlky bkoh^
gufb^bnn_j_gpbZevgufbmjZ\g_gbyfb
Mklhcqb\hklvklZpbhgZjguolhq_d HklZgh\bfky djZldh gZ l_j
fh^bgZfbq_kdboijbagZdZomklhcqb\hklbklZpbhgZjguo lhq_d k\hckl\Z
dhlhjuo[uebjZkkfhlj_gu\e_dpbyo±>himklbfqlh \ klZpbhgZj
ghf khklhygbb \hagbdeb \hafms_gby \ua\Z\rb_ hldehg_gby G; b G,
\_ebqbgkbebihlhdh\hl bo klZpbhgZjguo agZq_gbc ; b , HdZau
\Z_lky qlh \ kemqZ_ _keb gZqZevgh_ klZpbhgZjgh_ khklhygb_ [ueh mk
lhcqb\uflhijhba\_^_gb_\_ebqbg\hafms_gbcG,b G; ^he`gh [ulv
iheh`bl_evguf
G,G;!
Wlh y\ey_lky djbl_jb_f mklhcqb\hklb klZpbhgZjguo khklhygbc
\^Zeb hl jZ\gh\_kby H^gZdh ihemqblv h[sb_ l_jfh^bgZfbq_kdb_ djb
l_jbb gZijZ\e_gby ^\b`_gby d klZpbhgZjghfm khklhygbx ^Ze_dhfm hl
jZ\gh\_kby g_ m^Z_lky IjbqbgZ khklhbl \ ^_l_jfbgbklkdhf oZjZdl_j_
ih\_^_gbydbg_lbq_kdbokbkl_f^eydhlhjuoihgylb_wgljhibb\hleb
qb_ hl jZ\gh\_kguo g_ bf__l j_rZxs_]h agZq_gby ^ey ij_^kdZaZgby
gZijZ\e_gbyi_j_oh^guoijhp_kkh\
KhihklZ\bf oZjZdl_j
mklhcqb\hklb klZpbhgZjghc
lhqdb kh kl_i_gvx __ m^Z
e_gghklb hl iheh`_gby l_j
fh^bgZfbq_kdh]h
jZ\gh\_kby <[ebab jZ\gh\_
kby \hafh`gu lhevdh mklhc
qb\u_ klZpbhgZjgu_ lhqdb
lbiZ maeZ Ih f_j_ m^Ze_
gby hl jZ\gh\_kby [m^ml jZk
lb \_ebqbgu O b , jbk b kbkl_fZ fh`_l ihdbgmlv
h[eZklv ebg_cghc l_jfh^b
gZfbdb g_ l_jyy h[s_c mk
lhcqb\hklb
Wlhfm JbkAZ\bkbfhklvklZpbhgZjghcdhg
khhl\_lkl\m_l
lhqdZ p_gljZpbbdhfihg_glZhliZjZf_ljZD
mklhcqb\uc nhdmk <ha baf_jyxs_]hhldehg_gbyhljZ\gh\_kby
fh`gh h^gZdh qlh ijb m^Z
e_gbb hl jZ\gh\_kby \
kbkl_f_ gZklmibl [bnmjdZpbhggh_ baf_g_gb_ b \hagbdg_l g_mklhcqb
\hklv G_mklhcqb\u_ klZpbhgZjgu_ lhqdb dhlhjufb h[eZ^Z_l kbkl_fZ
\^ZebhljZ\gh\_kbyhlghkylkydk_^eZfbebg_mklhcqb\ufnhdmkZf
< lhqd_ [bnmjdZpbb ]^_ l_jy_lky mklhcqb\hklv ijhba\_^_gb_ G, G;
klZgh\blky hljbpZl_evguf G, G; qlh khhl\_lkl\m_l l_jfh^bgZfb
q_kdhfm ihjh]m ihy\e_gby g_mklhcqb\hklb \ kbkl_f_ <hagbdZ_l dZd
]h\hjyl l_jfh^bgZfbq_kdZy nemdlmZpby m\h^ysZy kbkl_fm hl g_mklhc
qb\hclhqdbdhlhjZybfh`_lklZlvijbqbghcjZkiZ^Zkbkl_fu H^gZdh
ijb hij_^_e_gguo agZq_gbyo iZjZf_ljh\ wlZ nemdlmZpby dZd [u ^Z_l
lheqhdi_j_\h^ysbckbkl_fmdgh\hfmkhklhygbxdhlhjhfmbi_j_^Z_l
ky mklhcqb\hklv GZijbf_j ihy\e_gb_ ij_^_evgh]h pbdeZ hdheh g_mk
lhcqb\h]h nhdmkZ <hagbdgh\_gbx ^bkkbiZlb\guo kljmdlmj \
jZkij_^_e_gguokbkl_fZolZd`_ij_^r_kl\m_lgZjmr_gb_ l_jfh^bgZfb
q_kdhcmklhcqb\hklb\^Zebhl jZ\gh\_kby GZdhg_p ljb]]_jgu_ i_j_oh
^u f_`^m mklhcqb\ufb klZpbhgZjgufb khklhygbyfb kf jbk ijhbkoh^yl gZ ]jZgbp_ mklhcqb\hklb gZ djb\hc klZpbhgZjguo khklhy
gbc dh]^Z gZjmrZ_lky l_jfh^bgZfbq_kdZy mklhcqb\hklv b kbkl_fZ kh
\_jrZ_lkdZqdhh[jZaguci_j_oh^f_`^mmklhcqb\ufbkhklhygbyfb
LZdbf h[jZahf l_jfh^bgZfbq_kdb_ ijbagZdb mklhcqb\hklb klZ
pbhgZjguokhklhygbckh\iZ^Zxlkkhhl\_lkl\mxsbfbfZl_fZlbq_kdbfb
ijbagZdZfb b fh]ml kem`blv bo ^hihegbl_evghc oZjZdl_jbklbdhc Gh
\^Zeb hl jZ\gh\_kby m`_ g_ kms_kl\m_l h[sbo l_jfh^bgZfbq_kdbo djb
l_jb_\ gZijZ\e_gby ^\b`_gby hldjulhc kbkl_fu ihkdhevdm __ ih\_^_
gb_hij_^_ey_lky^bgZfbq_kdbfbk\hckl\Zfbbf_oZgbafZfbj_]meypbb
Zg_h[sbfbklZlbklbq_kdbfbaZdhghf_jghklyfb WlZ hkh[_gghklv h[m
keh\eb\Z_llZd`_bkeh`ghklv ijbf_g_gby ihgylbc wgljhibb b bgnhj
fZpbbijbhibkZgbbh[sbok\hckl\[bheh]bq_kdbokbkl_f
Wgljhiby b bgnhjfZpby Kh]eZkgh nhjfme_ ;hevpfZgZ wgljh
iby hij_^_ey_lky dZd eh]Zjbnf qbkeZ fbdjhkhklhygbc \hafh`guo \
^ZgghcfZdjhkdhibq_kdhckbkl_f_
6 N;OQ:
]^_ N; ˜± wj]˜]jZ^± beb ˜± wgljhibcguo _^bgbp
w_ dZe˜]jZ^± >`Dbeb ˜± >`D ± ihklhyggZy ;hevp
fZgZ:±qbkehfbdjhkhklhygbcgZijbf_jqbkehkihkh[h\dhlhjufb
fh`gh jZaf_klblv fhe_dmeu ]ZaZ \ khkm^_ Bf_ggh \ wlhf kfuke_ wg
ljhiby_klvf_jZg_mihjy^hq_gghklbboZhlbaZpbbkbkl_fu<j_Zevguo
kbkl_fZokms_kl\mxl mklhcqb\u_ b g_mklhcqb\u_ kl_i_gb k\h[h^u GZ
ijbf_j l\_j^u_ kl_gdb khkm^Z b fhe_dmeu aZdexq_ggh]h \ g_f ]ZaZ
Ihgylb_ wgljhibb k\yaZgh bf_ggh k g_mklhcqb\ufb kl_i_gyfb ih dh
lhjuf\hafh`gZoZhlbaZpby kbkl_fu Z qbkeh \hafh`guo fbdjhkhklhy
gbc gZfgh]h [hevr_ _^bgbpu < iheghklvx mklhcqb\uo kbkl_fZo
j_Zebam_lky lhevdh h^gh±_^bgkl\_ggh_ j_r_gb_ l_ qbkeh kihkh[h\
dhlhjufb hkms_kl\ey_lky wlh _^bgkl\_ggh_ fZdjhkhklhygb_ kbkl_fu
jZ\gh_^bgbp_: OZwgljhibyjZ\gZgmex<[bheh]bbbkihevah\Zlv
ihgylb_wgljhibbZ lZd`_ b l_jfh^bgZfbq_kdb_ ij_^klZ\e_gby fh`gh
lhevdh ih hlghr_gbx d dhgdj_lguf f_lZ[hebq_kdbf ijhp_kkZf Z g_
^eyhibkZgby\p_ehfih\_^_gbybh[s_[bheh]bq_kdbo k\hckl\ hj]Zgba
fh\K\yavwgljhibbbbgnhjfZpbb\l_hjbbbgnhjfZpbb[ueZmklZgh\
e_gZ^eyklZlbklbq_kdbokl_i_g_ck\h[h^u>himklbfqlhfu ihemqbeb
bgnhjfZpbxhlhfdZdbfdhgdj_lghkihkh[hf ba \k_o \hafh`guo kih
kh[h\hkms_kl\e_gh^Zggh_fZdjhkhklhygb_kbkl_fuHq_\b^ghdhebq_
kl\hbgnhjfZpbbdhlhjh_fuijbwlhfihemqZeb[m^_ll_f[hevr_q_f
[hevr_[ueZbkoh^gZyg_hij_^_e_gghklvbebwgljhibykbkl_fu
Kh]eZkgh l_hjbb bgnhjfZpbb \ wlhf ijhklhf kemqZ_ dhebq_kl\h
bgnhjfZpbbh_^bgkl\_gghfj_Zevghfkhklhygbbkbkl_fu[m^_ljZ\gh
, ORJ:
AZ _^bgbpm dhebq_kl\Z bgnhjfZpbb [bl ijbgbfZ_lky bgnhjfZ
pby kh^_j`ZsZyky \ ^hklh\_jghf khh[s_gbb dh]^Z qbkeh bkoh^guo
\hafh`guokhklhygbc[uehjZ\gh: , ORJ O[bl
GZijbf_jkhh[s_gb_hlhfgZdZdmxklhjhgm miZeZ fhg_lZ ijb [jhkZ
gbb \ \ha^mo kh^_j`bl dhebq_kl\h bgnhjfZpbb \ [bl KhihklZ\eyy
nhjfmeubfh`ghgZclbk\yavf_`^mwgljhib_c\wgljhibc
guo_^bgbpZobbgnhjfZpb_c\[blZo
6w_ ˜± [bl
L_i_jv ihiulZ_fky nhjfZevgh hp_gblv dhebq_kl\h bgnhjfZpbb
kh^_j`Zs_cky\l_e_q_eh\_dZ]^_bf__lkyde_lhdKihfhsvxnhj
fmeuihemqbf\_ebqbgm
, ORJaORJa˜[bl
LZdh_dhebq_kl\hbgnhjfZpbbg_h[oh^bfh[ueh[ubkoh^ghihem
qblvqlh[u hkms_kl\blv _^bgkl\_ggh ijZ\bevgh_ jZkiheh`_gb_ de_lhd
\ hj]Zgbaf_ Wlhfm wd\b\Ze_glgh \_kvfZ g_agZqbl_evgh_ kgb`_gb_ wg
ljhibbkbkl_fugZ
'6 ˜˜˜aw_a˜>`D
?keb kqblZlv qlh \ hj]Zgbaf_ hkms_kl\ey_lky lZd`_ mgbdZevguc
oZjZdl_jjZkiheh`_gbyZfbghdbkehlguohklZldh\\[_edZobgmde_hlb^
guohklZldh\\>GDlhh[s__dhebq_kl\hbgnhjfZpbbkh^_j`Zs_cky \
l_e_q_eh\_dZkhklZ\bl
,a˜[bl
qlhwd\b\Ze_glghg_[hevrhfmihgb`_gbxwgljhibbgZ'6aw_ >`D < ijhp_kkZo f_lZ[hebafZ wlh kgb`_gb_ wgljhibb e_]dh dhfi_g
kbjm_lky m\_ebq_gb_f wgljhibb ijb hdbke_gbb fhe_dme ]exdhau
LZdbfh[jZahfkhihklZ\e_gb_nhjfmebihdZau\Z_lqlh[bh
eh]bq_kdb_ kbkl_fu g_ h[eZ^Zxl dZdhceb[h ih\ur_gghc bgnhjfZpb
hgghc _fdhklvx ih kjZ\g_gbx k ^jm]bfb g_`b\ufb kbkl_fZfb
khklhysbfb ba lh]h `_ qbkeZ kljmdlmjguo we_f_glh\ Wlhl \u\h^ gZ
i_j\uc\a]ey^ijhlb\hj_qbljhebbagZq_gbxbgnhjfZpbhgguoijhp_k
kh\\[bheh]bb
H^gZdhk\yavf_`^m,b6\kijZ\_^eb\Zebrvihhlghr_gbxd
bgnhjfZpbbhlhfdZdh_ba\k_o:fbdjhkhklhygbcj_Zebah\Zgh \ ^Zg
guc fhf_gl WlZ fbdjhbgnhjfZpby k\yaZggZy k jZkiheh`_gb_f \k_o
Zlhfh\\kbkl_f_gZkZfhf^_e_g_fh`_l[ulvaZihfg_gZ b khojZg_gZ
ihkdhevdmex[h_balZdbofbdjhkhklhygbc[ukljhi_j_c^_l\^jm]h_ba
aZ l_ieh\uo nemdlmZpbc : p_gghklv [bheh]bq_kdhc bgnhjfZpbb hij_
^_ey_lkyg_dhebq_kl\hfZij_`^_\k_]h\hafh`ghklvx__aZihfbgZgby
ojZg_gby i_j_jZ[hldb b ^Zevg_cr_c i_j_^Zqb ^ey bkihevah\Zgby \
`bag_^_yl_evghklbhj]ZgbafZ
2kgh\gh_ mkeh\b_ \hkijbylby b aZihfbgZgby bgnhjfZpbb ± wlh
kihkh[ghklv j_p_ilhjghc kbkl_fu \ke_^kl\b_ ihemq_gghc bgnhjfZpbb
i_j_oh^blv\h^ghbamklhcqb\uokhklhygbcaZjZg__aZ^Zgguo\ kbem __
hj]ZgbaZpbb Ihwlhfm bgnhjfZpbhggu_ ijhp_kku \ hj]Zgbah\Zgguo
kbkl_fZo k\yaZgu lhevdh k hij_^_e_ggufb kl_i_gyfb k\h[h^u KZf
ijhp_kk aZihfbgZgby bgnhjfZpbb ^he`_g khijh\h`^Zlvky g_dhlhjhc
ihl_j_cwg_j]bb\j_p_ilhjghckbkl_f_^eylh]hqlh[uhgZfh]eZ\g_c
khojZgblvky^hklZlhqgh_\j_fybg_l_jylvky\ke_^kl\b_l_ieh\uonemd
lmZpbcBf_ggha^_kvbhkms_kl\ey_lkyij_\jZs_gb_fbdjhbgnhjfZpbb
dhlhjmx kbkl_fZ g_ fh]eZ aZihfgblv \ fZdjhbgnhjfZpbx dhlhjmx
kbkl_fZ aZihfbgZ_l ojZgbl b aZl_f fh`_l i_j_^Zlv ^jm]bf Zdp_ilhj
guf kbkl_fZf DZd ]h\hjyl wgljhiby _klv f_jZ fgh`_kl\Z g_aZihfb
gZ_fuo kbkl_fhc fbdjhkhklhygbc Z fZdjhbgnhjfZpby ± f_jZ
fgh`_kl\Zbokhklhygbchij_[u\Zgbb\ dhlhjuo kbkl_fZ ^he`gZ ihf
gblv
GZijbf_j bgnhjfZpbhggZy _fdhklv \ >GD hij_^_ey_lky lhevdh
dhebq_kl\hf hij_^_e_gguo gmde_hlb^h\ Z g_ h[sbf qbkehf fbdjhkh
klhygbc \dexqZxsbo dhe_[Zgby \k_o Zlhfh\ p_ihqdb >GD Ijhp_kk
aZihfbgZgby bgnhjfZpbb \ >GD wlh nbdkZpby hij_^_e_ggh]h jZkih
eh`_gby gmde_hlb^h\ dhlhjh_ mklhcqb\h \ke_^kl\b_ h[jZamxsboky ob
fbq_kdbo k\ya_c \ p_ihqd_ >Zevg_crZy i_j_^ZqZ ]_g_lbq_kdhc
bgnhjfZpbb hkms_kl\ey_lky \ j_amevlZl_ [bhobfbq_kdbo ijhp_kkh\ \
dhlhjuo ^bkkbiZpby wg_j]bb b h[jZah\Zgb_ khhl\_lkl\mxsbo
mklhcqb\uoobfbq_kdbokljmdlmjh[_ki_qb\Z_lwnn_dlb\ghklv[bheh]b
q_kdhc i_j_jZ[hldb bgnhjfZpbb < p_ehf bgnhjfZpbhggu_ ijhp_kku
rbjhdh jZkijhkljZg_gu \ [bheh]bb GZ fhe_dmeyjghf mjh\g_ hgb ijh
l_dZxlg_lhevdhijbaZihfbgZgbb b i_j_jZ[hld_ ]_g_lbq_kdhc bgnhj
fZpbb gh b ijb \aZbfghf magZ\Zgbb fZdjhfhe_dme h[_ki_qb\Zxl
ki_pbnbqghklv b gZijZ\e_gguc oZjZdl_j n_jf_glZlb\guo j_Zdpbc
bf_xl \Z`gh_ agZq_gb_ ijb \aZbfh^_ckl\bb de_lhqguo f_f[jZg b ih
\_joghkl_c Nbabheh]bq_kdb_ j_p_ilhjgu_ ijhp_kku b]jZxsb_ kZfh
klhyl_evgmx bgnhjfZpbhggmx jhev \ `bag_^_yl_evghklb hj]ZgbafZ
lZd`_ hkgh\Zgu gZ \aZbfh^_ckl\byo fZdjhfhe_dme <h \k_o kemqZyo
fZdjhbgnhjfZpby\hagbdZ_lbkoh^gh\ \b^_ dhgnhjfZpbhgguo baf_g_
gbcijb^bkkbiZpbbqZklbwg_j]bbihhij_^_e_gguf kl_i_gyf k\h[h^u
\h\aZbfh^_ckl\mxsbofZdjhfhe_dmeZo<j_amevlZl_fZdjhbgnhjfZpby
hdZau\Z_lkyaZibkZgghc\\b^_ gZ[hjZ ^hklZlhqgh wg_j]_lbq_kdb ]em[h
dbo dhgnhjfZpbhgguo ih^khklhygbc dhlhju_ iha\heyxl khojZgylv wlm
bgnhjfZpbx\l_q_gb_\j_f_gbg_h[oh^bfh]h^ey__^Zevg_cr_ci_j_
jZ[hldb;bheh]bq_kdbckfukewlhc fZdjhbgnhjfZpbb j_Zebam_lky m`_
\khhl\_lkl\bb k hkh[_gghklyfb hj]ZgbaZpbb [bheh]bq_kdhc kbkl_fu b
dhgdj_lgufb de_lhqgufb kljmdlmjZfb gZ dhlhjuo jZau]ju\Zxlky
^Zevg_crb_ijhp_kkuijb\h^ysb_\blh]_dkhhl\_lkl\mxsbfnbabheh
]h[bhobfbq_kdbfwnn_dlZf
Download