実験報告書様式（一般利用課題・成果公開利用）
提出日 Date of Report

MLF Experimental Report

2014/7/13

課題番号 Project No.

装置責任者 Name of responsible person

2014A0194

Toshiya Otomo

実験課題名 Title of experiment

装置名 Name of Instrument/（BL No.）

The determination of mixing state of binary solution in confined

BL21

space

実施日 Date of Experiment

実験責任者名 Name of principal investigator

2014.05.21 21:00 - 2014.05.24 10:00

Taku Iiyama
所属 Affiliation
Faculty of Science, Shinshu University
試料、実験方法、利用の結果得られた主なデータ、考察、結論等を、記述して下さい。（適宜、図表添付のこと）
Please report your samples, experimental method and results, discussion and conclusions. Please add figures andtables for better explanation.
1. 試料 Name of sample(s) and chemical formula, or compositions including physical form.
A new designed measurement cell which keeps a hermetically closed condition was used for BL21
measurement. The ground activated carbon fiber A10 (Ad’all Co. Ltd.; pore width is 0.82 nm) was used asadsorbent.

We measured the ND of water-ethanol mixture on both of bulk and adsorbed states. The

molar fraction of water w = 0 (pure ethanol), 0.3, 0.6, 0.9, 1.0 (pure water). The deuterium substitution
samples, C2D5OD and D2O were used as adsorbate for reduction the recoil factor. Adsorbed amounts on A10
were controlled at near of saturated adsorbed amount ( = 0.9). The measurement times were 160 m forbulk samples, and 300 m for adsorbed conditions, respectively.

2. 実験方法及び結果 （実験がうまくいかなかった場合、その理由を記述してください。）
Experimental method and results.

If you failed to conduct experiment as planned, please describe reasons.

For adsorbed condition samples, the carbon sample
introduced in the cell of 10 mm diameter, and preheatedfor 8 h at 383 K and 1 mPa before the measurements.
Then each adsorbate was introduced via vapor with theadsorbed amount controlling.

The sample cells werehermetically closed, and keep over 3 days for theequilibrium. For bulk samples, cell of 6 mm diameter wasused.
Fig. 1 show the ND profiles of adsorbed phases by using
45 º bank data.

These data were obtained by thesubtraction of ND profiles of carbon sample itself (atvacuum condition) from that of adsorbed conditions.

Fig.1 ND profiles of adsorbed phases12. 実験方法及び結果（つづき） Experimental method and results (continued)
All data show the broad peak feature due to the liquid likestructures of adsorbed phases. The subtraction of carbon
peaks well done.

It can be confirmed smooth profile

feature and continuous and systematic change of profiles
with molar fraction of mixture.
We can compared these adsorbed data with the mixture
on bulk condition. In the high Q region (Q > 8 A-1), bothprofiles are almost coincide. It indicates that the shortrange structure such as intramolecular structure of waterand ethanol does not change in the micropore. However,the low Q peaks show the distinguish changes.

Fig. 2show the structure factors of various molar fraction ofmixture on the adsorbed and bulk conditions. Solid lines
denote the adsorbed, and broken lines denote the bulk
conditions, respectively. On the water rich fractions (w =Fig.2 Comparing of structure factors ofadsorbed (solid line) and bulk conditions(broken line).

1.0, 0.9), the main peak of structure factors are shift to thelow Q side, and intensity increases apparently. On theother hand, the main peaks of ethanol rich fractions (w =0.0, 0.3) shift to the high Q side. These results suggest
the sparse structure of water, and dense structure ofethanol in the micropore, respectively.
The radial distribution functions (RDF) which wereobtained by Fourier transformation of structure factors
were shown in Fig. 3. In water rich cases, the peaks inshort range (r < 0.2 nm) denote the intramolecular
structure, and peaks at far from 0.2 nm denote theintermolecular structure of water. The main peak (at 0.4nm) come from the first and second nearest neighbormolecules, and this peak shift to long distance and intensity

Fig.3 Radial distribution functions ofadsorbed (solid line) and bulk conditions(broken line).

increase in bulk condition. Furthermore, amplitude of RDF around 3rd and 4th peaks are increase and also
shift to long distance. This result show the intermolecular structure of water including hydrogen bonding arestrongly affected by the space restriction. On the other hand, ethanol rich case, the main peak of RDF at 0.5
nm due to the first nearest neighbor molecules does not shift in the micropore, but 2nd and 3rd molecules
peaks shift to short distances.
We already measured of XRD data of same systems, and will compare soon. The detailed structure analysis
especially for mixture done using reverse Monte Carlo simulation. By the using of both of ND and XRD
profiles, the detailed structure especially hydrogen bonding of water and ethanol mixture should be elucidated.

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