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3.2.2. Laws of change of full energy in isomers H-H - (CSOH), H-Alk-CSH3, H-Alk-SO2?, SH - (CH2) n-S?, H-H - (CSO) *, H-H - (CS? 2) *, n-n - (-CH-CSOH) * and H-H - (SO2) *

Values E (R) in isomers of numbers CH3 - (CH2) n-CSOK, CH3 - (CH2) n - (CSO) *, CH3 - (CH2) n-SO2K, CH3 - (CH2) n - (SO2) ∙, CH3 - (CH2) n-CSK3, CH3 - (CH2) n - (CSK2) *, HS - (CH2) n-SH, and CH3 - (CH2) n - (CH-CSOK) * where 0 ≤ n ≤ 10, are presented in tables 3.

Calculations of all studied molecules and radicals are executed by one method with an identical basic set of functions.

Equal values Ξ (R) alkilnyh fragments sulphur-containing organicheyoskih connections CH3 - (CH2) n, where 4 ≤ n ≤ 9 (tab. 3 see.), allow to aggregate homologous series in tables on isomers:

CH3 - (CH2) n-CSOK (tab. 3.2.2.3) and CH3 - (CH2) n - (CSO) * (tab. 3.2.2.9);

CH3 - (CH2) n-SO2K (tab. 3.2.2.4) and CH3 - (CH2) n - (SO2) ∙ (tab. 3.2.2.10);

CH3 - (CH2) n-CSK3 (tab. 3.2.2.5) and CH3 - (CH2) n - (CSK2) * (tab. 3.2.2.8);

HS - (CH2) n-SH (tab. 3.2.2.6);

CH3 - (CH2) n - (-CH-CSOK) * (tab. 3.2.2.7).

Within one point (and, and), at 4 ≤ n (tab. 3, 3.2.2.8­3.2.2.10), are noted equal values energy СН3, and also СН2, not subject to inductive influence R. Presence of free valency in (tab. 3.2.2.7) dayoet possibility to compare influence of fragments (CSOH), (CH-CSOH) * and (CSO) * on energy СН3 and СН2 a carbon backbone chain, and absence of isomers in a case (tab. 3.2.2.6) does not allow to make such comparison.

Energy of groups of all considered alkilnyh fragments of connections CH3 (CH2) n - (CH2) 2R, with 2 ≤ n ≤ 6 is presented in table 3.2.2.1.

Table 3.2.2.1.: Energy E (R) groups Ch3i Ch2v CH3 (CH2) n - (CH2) 2R, in a.e.

n CH3 CH2 CH2 CH2 CH2 CH2 CH2
R = C (O) SiiH, C (Sii)-OH, C? S ιv-0H, CH=S v=0, C? SH =0, (-C=SH2) ∙, (-CH=SH) * CH2-S11H
2 39,822 39,206 - - - - 39,224
3 39,827 39,214 - - - 39,228 39,229
4 39,833 39,218 - - 39,235 39,232 39,234
5 39,838 39,224 - 39,239 39,239 39,236 39,238
6 39,842 39,228 39,242 39,243 39,243 39,240 39,242
R = Svi (O) CH, O-Sii-OH, Siv (O) OH, Svi (O) (O) H, C (O) S *, (-C? S=O) * (-S (O) O) *, (-O-S-O) *
2 39,819 39,204 - - - - 39,219
3 39,826 39,213 - - - 39,225 39,224
4 39,832 39,218 - - 39,234 39,230 39,228
5 39,837 39,223 - 39,238 39,238 39,234 39,233
6 39,842 39,227 39,243 39,242 39,241 39,238 39,237
R = (-CH-C (O) SH) *, (-CH-C (S) OH) *, (-CH-C? S-OH) *, CH=SivH2, (-CH-C? SH=O) *
2 39,825 39,211 - - - - 39,225
3 39,831 39,216 - - - 39,232 39,229
4 39,836 39,222 - - 39,237 39,236 39,233
5 39,841 39,226 - 39,242 39,240 39,239 39,238

The analysis electronic energy groups E (R) in a number-d) has shown:

1.

Inductive influence Rв CH3 - (CH2) n-R where 3 ≤ n ≤ 8, and SH in HS - (CH2) n-SH where 5 ≤ n ≤ 10, it it is reflected in changes of energy of two proximate CH2групп (otyolichajutsja from values "not revolted" CH2). At n ≤ 2///-effect Rв CH3 - (CH2) n-Rzatragivaet and E (CH3).

2. In CH3 - (CH2) n-R, where 4 ≤ n. At comparison E (R) groups of connections with identical alkilnym the substituent notes shipping of fragments - (CH2) 2-R.

3. In CH3 - (CH2) n-R where 4 ≤ n, in isomers of all connections E (CH3) are equal for iskljuyocheniem a case (tab. 3.). The Same phenomenon is noted and at "neyovozmushchyonnyh" CH2.

4. Within one homologous series equality of values E (CH3) and E (CH2) is observed. Not subject to inductive influence serosoderzhashcheej a functional group (tab. 3.2.2.1.). Therefore groups of such site dolzhyony to possess "shipping". However in different numbers calculations yield different E (CH3) and E (CH2) for alkilnyh fragments with identical n. Thus. At use in phenomenological models it is required masshtabirovayonie to full energy.

5. Introduction of "transferable" group CH2 and its energy can be carried out sleyodujushchem in the image. The difference (∆E) in Etotalмежду next gomoyologami of the same kind (in table 3.2.2.2 is calculated. Values Etotalи ∆Eдля moyolekul and radicals of different numbers) are resulted. ∆Eпоказывает. On how many decreases Etotal connections among at increase in chain length at one CH2. So. Occurrence of the first CH2в connections depresses size Etotalот 103230 kdzh/MOLE (for HS-CH2-SH and HS-SH, ∆E=39.318 a.e.) to 103290 kdzh/MOLE (from CH3 - (-(-C (O) SH) * to CH3-CH2 - (-CH-C (O) SH) *, ∆E=39.339 a.e.). Occurrence of the second CH2и the further elongation alkilnoj shows to a chain for all serosoderzhayoshchih molecules and their radicals of one size ∆E = 39.328 a.e. Hence. For the yielded method full energy of the next members of homologous series buyodet to differ on 103260 kdzh/MOLE - energy of "standard" group CH2.

6. In CH3 - (CH2) n-R. With 4 ≤ n ≤ 8. Identical alkilnye fragments seroorganicheyoskih connections bring the identical contribution to full energy. Hence. Their difference Etotalпри one value nв CH3 - (CH2) n-R (tabl 3.2.2.2.) opredeljayoetsja order of atoms in sulphur-containing groups Rizomera.

7. At comparison energy formally identical fragments CH3 - (CH2) n-S (O) in molecules CH3 - (CH2) n-S (O) CH (tab. 3.2.2.3.) and in CH3 - (CH2) n-S (O) OH (tab. 3.2.2.4.) with one length of a hydrocarbon chain their distinction Etotal.Та­ким is noted by image. Contributions of these fragments in Etotalсоединения also differ.

Table 3.2.2.2.:

Full energy Etotalмолекул and radicals, a difference in full energy between sosedyonimi homologues ∆E in a.e.

n CH3 - (CH2) N - (-CH-C (O) SH) * CH3 - (CH2) N -

C (O) S*

SH - (CH2) n-SH CH3 - (CH2) N - (-C=SH2) * CH3 - (CH2) n-SH
Etotal ∆E Etotal ∆E Etotal ∆E Etotal ∆E Etotal ∆E
ABOUT -551,472 - -551,492 - -797,656 - -437,983 - -438,754 -
1 -590,811 39,339 -590,820 39,328 -836,974 39,318 -477,313 39,330 -478,085 39,331
2 -630,139 39,327 -630,148 39,328 -876,303 39,329 -516,640 39,327 -517,413 39,328
3 -669,467 39,328 -669,476 39,328 -915,632 39,329 -555,968 39,328 -556,741 39,328
4 -708,795 39,328 -708,805 39,329 -954,961 39,329 -595,296 39,328 -596,069 39,328
5 -748,123 39,328 -748,132 39,327 -994,289 39,328 -634,623 39,327 -635,397 39,328
6 -787,451 39,328 -787,460 39,328 -1033,617 39,328 -673,951 39,328 -674,724 39,328
7 -826,779 39,328 -826,788 39,328 -1072,945 39,328 -713,280 39,329 -714,052 39,328
8 -866,107 39,328 -866,115 39,327 -1112,273 39,328 -752,608 39,328 -753,380 39,328
9 - - -905,444 39,329 -1151,601 39,328 -791,936 39,328 -792,708 39,328
R-O-S-OH R - (-O-S-O) * R-S (O) (O) H R - (-S (O) O) * R-S (O) CH
Etotal AE Etotal ∆E Etotal AE Etotal AE Etotal AE
ABOUT -589,22 - -588,610 - -589,227 - -588,606 - -551,983 -
1 -628,557 39,337 -627,953 39,344 -628,563 39,336 -627,943 39,337 -591,317 39,334
2 -667,886 39,329 -667,280 39,327 -667,891 39,328 -667,271 39,328 -630,646 39,329
3 -707,215 39,329 -706,608 39,328 -707,219 39,328 -706,599 39,328 -669,974 39,328
4 -746,542 39,327 -745,936 39,328 -746,547 39,328 -745,927 39,328 -709,302 39,328
5 -785,871 39,329 -785,264 39,328 -785,874 39,327 -785,255 39,328 -748,630 39,328
6 -825,198 39,327 -824,592 39,328 -825,202 39,328 -824,583 39,328 -787,958 39,328
7 -864,527 39,329 -863,920 39,328 -864,531 39,329 -863,911 39,328 -827,286 39,328
8 -903,854 39,327 -903,248 39,328 -903,859 39,328 -903,239 39,328 -866,614 39,328
9 - - - - -943,187 39,328 -942,567 39,328 -905,942 39,328

8. The comparative analysis of electronic properties of group with free valency CK* from CH3 - (CH2) n-CK*-CSOH (tab. 3.2.2.7 is carried out.) with CK, at a multiple bond in tialah CH3 - (CH2) n-CH=SH2 (tab. 3.2.2.5.) and their radicals CH3 - (CH2) n - CK=S*K (tab. 3.2.2.9.) Kачиная with n ≥ 1, values E (CK) in connections CH3 - (CH2) n-CH=SH2 (tab. 3.2.2.5.) and CH3 - (CH2) n-CK=S*K (tab. 3.2.2.9.) with odinakoyovym nочень are close on size (the difference makes no more than 8 kdzh/MOLE). Characteristic E (CK *) (tab. 3.2.2.7.) depends on structure CSOH (from vzaimoyoraspolozhenija atoms of sulphur, oxygen and carbon). So in case of C (S) OH and
C (O) SH energy E (CH *)> E (CH). Whereas in C? S-OH and C? SH=O the parity is revertive E (CH *) 3) with uvelicheyoniem nэнергия identical groups starts to decrease on same veliyochinu ∆E (R). Comparable with a margin error calculation (∆E (CH2) = 0.004 a.e. And ∆E (CH3) = 0.005 a.e. (Tab. 3.)).

During research it has been revealed. What is the influence serosoderyozhashchego fragment Rв CH3 - (CH2) n-R, where 0 ≤ n ≤ 9. R = C (O) SiiH, C (Sii)-OH, C? Siv-OH, CH=Siv=O, C? SviH=O, Svi (O) CH, Siv (O) OH, O-Sii-OH, Svi (O) (O) H, CH=SιvH2, CH2-S11H, (-CH-C (O) SH) *, (-CH-C (S) OH) *, (-CH-C? S-OH) *, (-C? S=O) *, (-CH-C? SH=O) *, C (O) S *, (-C=SH2) *, (-CH=SH) *, (-S (O) O) * and (-O-S-O) *. rasproyostranjaetsja on energy of two next CH2 groups. At fragmentirovanii soedineyony CH3 (CH2) n - (CH2) 2R. With 2 ≤ n ≤ 6. Difference Eгрупп in identical position in alkilnoj chains in relation to R, but in different homologues, makes no more than 10 kdzh/MOLE. At increase nна unit full energy of investigated molecules and radicals decreases for 103260 kdzh/MOLE (39.328 a.e.). In CH3 - (CH2) n-Rpri odyonom value nдля all connections Etotalопределяется by a structure serosoderzhayoshchej groups.

Table 3.2.2.3.:

Energy of groups-E (R) in molecules CH3 - (CH2) n-COSH, in a.e., where 0

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A source: Rusakova Natalia Petrovna. QUANTUM-CHEMICAL STUDY OF THE ELECTRONIC STRUCTURE OF SERO-CONTAINING MOLECULES AND RADICALS. DISSERTATION for the degree of Candidate of Chemical Sciences. Tver - 2015. 2015

More on topic 3.2.2. Laws of change of full energy in isomers H-H - (CSOH), H-Alk-CSH3, H-Alk-SO2?, SH - (CH2) n-S?, H-H - (CSO) *, H-H - (CS? 2) *, n-n - (-CH-CSOH) * and H-H - (SO2) *:

  1. volumes of groups in n-Alk-CSH3, n-Alk-SO2H, SH - (CH2) n-SH, n-n - (-CH-CSOH) ∙, n-n - (CSH2) *, n-n - (SQ2) *,//-IlA - (CSO) *, and n-Alk-CSOH
  2. geometry and oscillatory frequencies of structure isomerides CSO? 2, SO2? 2 CS? 4, and their radicals (CSOH) ’, (SCHI) ’, (CSH3) ’
  3. inductive influence of various sulphur-containing groups on charges of fragments of hydrocarbon chains in molecules and radicals: H-H - (CSOO) W, p-A1kSn3, a-Alk-SOi^8Н-(СН2).-8ІН n-n - (-CSO) *, n-n - (-CSR) *, W-Alk-GCH-CSOR* and P-p - (^ About і)*
  4. an electronic structure of isomers CSOH2, CSH4, SO2H2и their radicals (CSOH) ’, (CSH3 ’), (SO2H) ’
  5. studying of a conformational variety of isomers CH3-CSOH
  6. Influence of sulphur-containing fragments on a charge of groups, reference spinoyovoj density in radicals H-H - (SO2) *
  7. calculation of full energy of modelling molecules.
  8. methods definition of full energy of a molecule.
  9. experimental researches of change of the specific expense of electric energy and quality indicators of process of mixture from is constructive-technological parametres
  10. §1. Legal features of the market of electric energy. The consumer of electric energy as the subject of relations on supply by electric energy
  11. studying of the phenomenon of internal rotation in gosh isomers n - mononitroalkanov