• Korean Journal of Materials Research
• /
• v.20 no.3
• /
• pp.111-116
• /
• 2010

Chloride-based fluxes such as NaCl-KCl are used in the refining of Al melt. The vapor pressure of the chloride is one of the fundamental pieces of information required for such processes, and is generally high at elevated temperatures. In order to measure the vapor pressure for chlorides, the apparatus for the transpiration method was assembled in the present study. The vapor pressure of $ZnCl_2$ and $FeCl_2$, which is related with the process of aluminum refining and the recovery of useful elements from iron and steel industry by-products, was also measured. In the measurement of vapor pressure by the transpiration method, the powder of $ZnCl_2$ or $FeCl_2$ in a alumina boat was loaded in the uniform zone of the furnace with a stream of Ar. The weight loss of $ZnCl_2$ and $FeCl_2$ after holding was measured by changing the flow rate of Ar gas (10 sccm -230 sccm), and the partial pressures of $ZnCl_2$ and $FeCl_2$ were calculated. The partial pressures within a certain range were found to be independent of the flow rate of Ar at different temperatures. The vapor pressures were measured in the temperature range of 758-901K for $ZnCl_2$ and 963-983K for $FeCl_2$. The measured results agreed well with those in the literature.

• Applied Chemistry for Engineering
• /
• v.9 no.5
• /
• pp.698-703
• /
• 1998

The pervaporation experiments of aqueous solutions of trichloroethylene (TCE) and chlorobenzene (CB) through the silicone rubber (polydimethylsiloxane, PDMS) membrane were carried out and the effect of concentration polarization on the separation characteristics was investigated. The resistance-in-series model was used to explain the boundary layer resistance. It was clear that the concentration polarization phenomenon had a significant effect on the permeation behavior in the pervaporation separation of the trace organic chlorides from aqueous solutions. With the same membrane thickness, the permeation of TCE, which has a stronger affinity for the PDMS, appeared to be more influenced by the boundary layer resistance than that of CB. The effect of boundary layer resistance was reduced and the membrane resistance became dominant with increasing membrane thickness at a given hydrodynamic condition. The separation factor was increased to approach the intrinsic separation factor of the membrane with its thickness.

• Bulletin of the Korean Chemical Society
• /
• v.4 no.1
• /
• pp.3-9
• /
• 1983

Lithium n-butylborohydride was prepared from borane-dimethylsulfide (BMS) and n-butyllithium, and the approximate rates and stoichiometrics of its reactions with selected organic compounds containing representative functional groups were studied in THF at room temperature. Phenol and benzenetiol liberated hydrogen quickly and quantitatively, and the reactions of primary alcohols, 2,6-di-ter-butylphenol and 1-hexanethiol liberated hydrogen quantitatively within 3 hrs, whereas the reactions of secondary and tertiary alcohols were very slow. Aldehydes and ketones were reduced rapidly and quantitatively to the corresponding alcohols. Cinnamaldehyde utilized 1 equiv. of hydride rapidly, suggesting the reduction to cinnamyl alcohol. Carboxylic acids evolved 1 equiv. of hydrogen rapidly and further reduction was not observed. Anhydrides utilized 2 equiv. of hydride rapidly but further hydride uptake was very slow, showing a half reduction. Acid chlorides were reduced to the alcohol stage very rapidly. All the esters examined were reduced to the corresponding alcohol rapidly. Lactones were also reduced rapidly. Expoxides took up 1 equiv. of hydride at a moderate rate to be reduced to the corresponding alcohols. Nitriles and primary amides were inert to this hydride system, whereas tertiary amide underwent slow reduction. Nitroethane and nitrobenzene were reduced slowly, however azobenzene and azoxybenzene were quite inert. Cyclohexanone oxime evolved 1 equiv. of hydrogen rapidly, but no further reduction was observed. Phenyl isocyanate and pyridine N-oxide were proceeded slowly, showing 1.74 and 1.53 hydride uptake, respectively in 24 hours. Diphenyl disulfide was reduced rapidly, whereas di-n-butyl disulfide, sulfone and sulfonic acids were inert or sluggish. n-Hexyl iodide and benzyl bromide reacted rapidly, but n-octyl bromide, n-octyl chloride, and benzyl chloride reacted very slowly.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.2
• /
• pp.132-138
• /
• 1994

Bis(diethylamino)aluminum hydride was utilized in a systematic study of the approximate rates and stoichiometry of the reaction of excess reagent with 55 selected organic compounds containing representative functional groups under standardized conditions (THF, $0^{\circ}C$, reagent to compound=4 : 1) in order to define the characteristics of the reagent for selective reductions. The reducing action of BEAH was also compared with that of the parent aluminum hydride. The reducing action of the reagent is quite similar to that of aluminum hydride, but the reducing power is much weaker. Aldehydes and ketones were readily reduced in 1-3 h to the corresponding alcohols. However, unexpectedly, a ready involvement of the double bond in cinnamaldehyde was realized to afford hydrocinnamyl alcohol. The introduction of diethylamino group to the parent aluminum hydride appears not to be appreciably influential in stereoselectivity on the reduction of cyclic ketones. Both p-benzoquinone and anthraquinone utilized 2 equiv of hydride readily without evolution of hydrogen, proceeded cleanly to the 1,4-reduction products. Carboxylic acids and acid chlorides underwent reduction to alcohols slowly, whereas cyclic anhydrides utilized only 2 equiv of hydride slowly to the corresponding hydroxylacids. Especially, benzoic acid with a limiting amount of hydride was reduced to benzaldehyde in a yield of 80%. Esters and lactones were also readily reduced to alcohols. Epoxides examined all reacted slowly to give the ring-opened products. Primary and tertiary amides utilized 1 equiv of hydride fast and further hydride utilization was quite slow. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Among them, benzamide and N,N-dimethylbenzamide gave ca, 90% yields of benzaldehyde. Both the nitriles examined were also slowly reduced to the amines. Unexpectedly, both aliphatic and aromatic nitro compounds proved to be relatively reactive to the reagent. On the other hand, azo- and azoxybenzenes were quite inert to BEAH. Cyclohexanone oxime liberated 1 equiv of hydrogen and utilized 1 equiv of hydride for reduction, corresponding to N-hydroxycyclohexylamine. Pyridine ring compounds were also slowly attacked. Disulfides were readily reduced with hydrogen evolution to the thiols, and dimethyl sulfoxide and diphenyl sulfone were also rapidly reduced to the sulfides.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.10
• /
• pp.873-881
• /
• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.10
• /
• pp.881-888
• /
• 1994

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.4
• /
• pp.382-388
• /
• 1989

The approximate rates and stoichiometry of the reaction of excess potassium tri-sec-butylborohydride ($K_s-Bu_3BH$) with selected organic compounds containing representative functional groups were determined under the standard conditions (0$^{\circ}C$, THF) in order to define the characteristics of the reagent for selective reductions. Primary alcohols evolve hydrogen in 1 h, but secondary and tertiary alcohols and amines are inert to this reagent. On the other hand, phenols and thiols evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to the corresponding alcohols. Reduction of norcamphor gives 99.3% endo- and 0.7% exo-isomer of norboneols. The reagent rapidly reduces cinnamaldehyde to the cinamyl alcohol stage and shows no further uptake of hydride. p-Benzoquinone takes up one hydride rapidly with 0.32 equiv hydrogen evolution and anthraquinone is cleanly reduced to the 9,10-dihydoxyanthracene stage. Carboxylic acids liberate hydrogen rapidly and quantitatively, however further reduction does not occur. Anhydrides utilize 2 equiv of hydride and acyl chlorides are reduced to the corresponding alcohols rapidly. Lactones are reduced to the diol stage rapidly, whereas esters are reduced moderately (3-6 h). Terminal epoxides are rapidly reduced to the more substituted alcohols, but internal epoxides are reduced slowly. Primary and tertiary amides are inert to this reagent and nitriles are reduced very slowly. 1-Nitropropane evolves hydrogen rapidly without reduction and nitrobenzene is reduced to the azoxybenzene stage, whereas azobenzene and azoxybenzene are inert. Cyclohexanone oxime evolves hydrogen without reduction. Phenyl isocyanate utilizes 1 equiv of hydride to proceed to formanilide stage. Pyridine and quinoline are reduced slowly, however pyridine N-oxide takes up 1.5 equiv of hydride in 1 hr. Disulfides are rapidly reduced to the thiol stage, whereas sulfide, sulfoxide, sulfonic acid and sulfone are practically inert to this reagent. Primary alkyl bromide and iodide are reduced rapidly, but primary alkyl chloride, cyclohexyl bromide and cyclohexyl tosylate are reduced slowly.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.4
• /
• pp.469-475
• /
• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(diethylamino)aluminum hydride (LTDEA) with selected organic compounds containing representative functional groups under standardized condition (tetrahydrofuran, 0$^{\circ}C$) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of LTDEA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(dibutylamino)aluminum hydride (LTDBA). In general, the reactivity toward organic functionalities is in order of LAH${\gg}$LTDEA${\geq}$LTDBA. LTDEA shows a unique reducing characteristics. Thus, benzyl alcohol and phenol evolve hydrogen slowly. The rate of hydrogen evolution of primary, secondary, and tertiary alcohols is distinctive: 1-hexanol evolves hydrogen completely in 6 h, whereas 3-hexanol evolves hydrogen very slowly. However, 3-ethyl-3-pentanol does not evolve any hydrogen under these reaction conditions. Primary amine, such as n-hexylamine, evolves only 1 equivalent of hydrogen. On the other hand, thiols examined are absolutely inert to this reagent. LTDEA reduces aldehydes, ketones, esters, acid chlorides, and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly, where as tertiary amides are readily reduced. Finally, sulfides and sulfoxides are reduced to thiols and sulfides, respectively, without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent to convert esters, primary carboxamides, and aromatic nitriles into the corresponding aldehydes. Free carboxylic acids are also converted into aldehydes through treatment of acyloxy-9-BBN with this reagent in excellent yields.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.5
• /
• pp.531-537
• /
• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• Journal of the Korea Institute of Building Construction
• /
• v.19 no.5
• /
• pp.383-389
• /
• 2019

The supply of natural aggregate for concrete has been difficult, and the amount of construction waste has been continuously increasing. Therefore, the necessity of using recycled aggregate made of construction waste as aggregate is rised. Therefore, many studies on the characteristics of concrete using recycled aggregate have been made and positive studies have been reported mainly in recent studies. A study on the chlorides binding effect of the mortar with recycled coarse aggregate has been reported. However, due to the user's perception of waste, most of the recycled aggregate currently produced is used only for low value-added products. In order to improve the recognition of recycled aggregate and the user's perception of recycled aggregate concrete, long-term monitoring of the structure with 100% recycled aggregate was conducted to confirm the applicability of the recycled aggregate concrete.