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Kuliah 7
Sifat-sifat Fisik Larutan

Definisi Larutan
Campuran homogen antara 2 macam zat atau lebih
Solut: jumlahnya lebih sedikit Solven: jumlahnya lebih banyak

Larutan terbentuk ketika partikel solven menarik partikel solut sehingga terpisah ke lingkungannya (terlarut)

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Beberapa Jenis Larutan

Larutan: Solut terdispersi dalam solven.

Konsentrasi Larutan
Kebanyakan konsentrasi dinyatakan dengan: Jumlah Solut Jumlah Solven atau Larutan

Molaritas: mole solut/liter larutan Persen massa: gram solut/gram larutan ( 100%) Persen volum: milliliter solut/milliliter larutan ( 100%) Persen massa/volum: gram solut/milliliter larutan ( 100%)
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Contoh 1
How would you prepare 750 g of an aqueous solution that is 2.5% NaOH by mass?

Contoh 2
At 20 C, pure ethanol has a density of 0.789 g/mL and USP ethanol has a density of 0.813 g/mL. What is the mass percent ethanol in USP ethanol?

Konsentrasi Larutan
Kebanyakan konsentrasi dinyatakan dengan: Jumlah Solut Jumlah Solven atau Larutan

Parts per million (ppm): gram solut/gram larutan (106 atau 1 juta) Parts per billion (ppb): gram solut/gram larutan (109 atau 1 miliar) Parts per trillion (ppt): gram solut/gram 12 atau ppm, ppb, ppt untuk menyatakan konsentrasi yang sangat larutan (10 1 triliun)
rendah (1 L air yang berisi 1 ppm fluoride mengandung 1 mg F)

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Contoh 3
The maximum allowable level of nitrates in drinking water in the United States is 45 mg NO3/L. What is this level expressed in parts per million (ppm)?

Konsentrasi Larutan
Kebanyakan konsentrasi dinyatakan dengan: Jumlah Solut Jumlah Solven atau Larutan

Molalitas (m): mole solut/kilogram solven. Molaritas tergantung pada temperatur (ekspansi dan kontraksi larutan). Molalitas berdasarkan pada massa solven (bukan larutan) dan tidak tergantung pada temperatur. Molalitas dapat digunakan untuk menyatakan beberapa sifat larutan

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Contoh 4
What is the molality of a solution prepared by dissolving 5.05 g naphthalene [C10H8(s)] in 75.0 mL of benzene, C6H6 (d = 0.879 g/mL)?

Contoh 5
How many grams of benzoic acid, C6H5COOH, must be dissolved in 50.0 mL of benzene, C6H6 (d = 0.879 g/mL), to produce 0.150 m C6H5COOH?

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Contoh 6
An aqueous solution of ethylene glycol HOCH2CH2OH used as an automobile engine coolant is 40.0% HOCH2CH2OH by mass and has a density of 1.05 g/mL. What are the (a) molarity, (b) molality, and (c) mole fraction of HOCH2CH2OH in this solution?

Contoh 7
Without doing detailed calculations, determine which aqueous solution has the greatest mole fraction of CH3OH: (a) 1.0 m CH3OH, (b)10.0% CH3OH by mass, or (c) xCH3OH = 0.10.

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Konsentrasi Larutan
Kebanyakan konsentrasi dinyatakan dengan: Jumlah Solut Jumlah Solven atau Larutan

Fraksi mol (xi): mol komponen i per mol seluruh komponen (larutan). Jumalah fraksi-fraksi mol untuk seluruh komponen dalam suatu larutan sama dengan _______? Persen mol: fraksi mol 100%.

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Entalpi Larutan
Pembentukan larutan dapat digambarkan dalam 3 langkah: 1. Pergerakan molekul-molekul solven saling menjauh untuk memberi ruang pada molekul solut. H1 > 0 (endotermis) 2. Pemisahan molekul-molekul solut untuk menuju ke dalam larutan. H2 > 0 (endotermis) 3. Pencampuran molekul-molekul solut dan solven yang telah saling terpisah untuk bercampur secara acak. H3 < 0 (eksotermis) Hsoln = H1 + H2 + H3

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Diagram Entalpi Pelarutan

For dissolving to occur, the magnitudes of H1 + H2 and of H3 must be roughly comparable.

Gaya Antar Molekul pada Pembentukan Larutan

Suatu larutan ideal terbentuk jika semua gaya anata molekul seimbang, Hsoln = 0. Jika gaya antar molekul solut-solven lebih kuat dari gaya antar molekul yang lain, Hsoln < 0. Jika gaya antar molekul solut-solven lebih lemah dari gaya antar molekul yang lain, Hsoln > 0. Jika gaya antar molekul solut-solven jauh lebih lemah dari gaya antar molekul yang lain, solut tidak terlarut ke dalam solven. Energi yang dilepaskan oleh interaksi solutsolven tidak cukup besar untuk meisahkan partikel solut atau partikel solven.
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Gaya Antar Molekul dalam Larutan

For a solute to dissolve, the strength of solvent solvent forces

must be comparable to solute solvent forces. and solute solute forces

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Larutan Non Ideal

when mixed, give less than 100 mL of solution.

50 mL of ethanol

and 50 mL of water

In this solution, forces between ethanol and water are _____er than other intermolecular forces.

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Larutan Senyawa Ionik dalam Air

Gaya yang menyebabkan kelarutan padatan ionik dalam air adalah gaya iondipol, gaya tarik air memiliki 2 kutub, untuk kation dan anion. Gaya tarik dua kutub untuk air menarik ion keluar dari kristalnya menuju larutan dalam air. Kemampuan suatu padatan ionik untuk terlarut dalam air ditentukan oleh gaya tarik menarik antara: Gaya tarik antar ion yang mengikat ion dalam kristalnya Gaya tarik iondipol yang menarik ion ke dalam larutan

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Gaya IonDipol pada Pelarutan

Negative ends of dipoles attracted to cations.

Positive ends of dipoles attracted to anions.

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Contoh 8
Predict whether each combination is likely to be a solution or a heterogeneous mixture: (a) methanol, CH3OH, and water, HOH (b) pentane, CH3(CH2)3CH3, and octane, CH3(CH2)6CH3 (c) sodium chloride, NaCl, and carbon tetrachloride, CCl4 (d) 1-decanol, CH3(CH2)8CH2OH, and water, HOH

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Beberapa Istilah dalam Kelarutan

Cairan yang dapat tercampur seluruhnya dinamakan miscible. Jika terdapat kesetimbangan dinamik antara solut yang tidak terlarut dengan larutan, maka larutan dikatakan saturated (jenuh) Konsentrasi solut dalam larutan jenuh dinamakan solubility (kelarutan) solut tersebut. Larutan yang mengandung lebih sedikit solut daripada yang dapat dikandung pada saat kesetimbangan dinamakan larutan unsaturated (tak jenuh).

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Pembentukan Larutan Jenuh

Solid begins to dissolve. Eventually, the rates of dissolving and of crystallization are equal; no more solute appears to dissolve.

As solid dissolves, some dissolved solute begins to crystallize.

Longer standing does not change the amount of dissolved solute.

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Kelarutan Sebagai Fungsi Suhu

Semua senyawa ionik memiliki kelarutan dalam air yang akan meningkat secara signifikan dengan kenaikan temperatur. Beberapa memiliki kelarutan yang sedikit meningkat dengan kenaikan temperatur. Sangat sedikit memiliki kelarutan yang menurun dengan kenaikan temperatur. Jika kelarutan meningkat terhadap temperatur, suatu larutan yang jenuh dan panas dapat didinginkan tanpa adanya pengendapat solut. Larutan tersebut dinamakan larutan supersaturated (lewat jenuh). Larutan lewat jenuh biasanya tidak stabil

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Larutan Lewat Jenuh

A single seed crystal of solute is added. Solute immediately begins to crystallize until all of the excess solute has precipitated.

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Kurva Kelarutan

What is the (approx.) solubility of KNO3 per 100 g water at 90 C? At 20 C?

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Kristalisasi Selektif

When KNO3(s) is crystallized from an aqueous solution of KNO3 containing CuSO4 as an impurity, CuSO4 (blue) remains in the solution.
KNO3 crystallized from a hot, saturated solution is virtually pure.

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Kelarutan Gas
Kebanyakan gas menjadi kurang larut dalam cairan jika temperatur meningkat. (Mengapa?) Pada temperatur konstan, kelarutan (S) gas proporsional terhadap tekanan gas (Pgas) dalam kesetimbangan dengan larutan. S = k Pgas Nilai k tergantung pada jenis gas dan solven. Pengaruh tekanan terhadap kelarutan gas dikenal sebagai Henrys law.

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Pengaruh Temperatur Terhadap Kelarutan Gas

Thermal pollution: as river/lake water is warmed (when used by industry for cooling), less oxygen dissolves, and fish no longer thrive.

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Tekanan dan Kelarutan Gas

Higher partial pressure means more molecules of gas per unit volume

thus more frequent collisions of gas molecules with the surface

giving a higher concentration of dissolved gas.

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Contoh 9
A 225-g sample of pure water is shaken with air under a pressure of 0.95 atm at 20 C. How many milligrams of Ar(g) will be present in the water when solubility equilibrium is reached? Use data from Figure 12.14 and the fact that the mole fraction of Ar in air is 0.00934.

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Sifat Koligatif Larutan

Sifat Koligatif suatu larutan hanya tergantung pada konsentrasi partikel solut, tidak tergantung pada sifat-sifat solut. Sifat Non-koligatif termasu: bau, warna, massa jenis, viskositas, toksisitas, reaktivitas, dsb. Dalam kuliah ini akan dipelajari 4 sifat koligatif larutan: Tekanan uap (solven) Penurunan titik beku Kenaikan titik didih Tekanan osmotik

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Tekanan Uap Larutan

Tekanan uap suatu solven di atas suatu larutan lebih rendah daripada tekan uap solven di atas solven murni. Raoults law: tekanan uap suatu solven di atas suatu larutan (Psolv) adalah produk dari tekanan uap solven murni (Psolv) dan fraksi mol solven dalam larutan (xsolv): Psolv = xsolv Psolv Uap yang berada dalam kesetimbangan larutan ideal anatara dua komponen volatil memiliki fraksi molar yang lebih tinggi untuk komponen yang lebih volatil daripada fraksi di dalam cairan.

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Contoh 10
The vapor pressure of pure water at 20.0 C is 17.5 mmHg. What is the vapor pressure at 20.0 C above a solution that has 0.250 mol sucrose (C12H22O11) and 75.0 g urea [CO(NH2)2] dissolved per kilogram of water?

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Contoh 11
At 25 C, the vapor pressures of pure benzene (C6H6) and pure toluene (C7H8) are 95.1 and 28.4 mmHg, respectively. A solution is prepared that has equal mole fractions of C7H8 and C6H6. Determine the vapor pressures of C7H8 and C6H6 and the total vapor pressure above this solution. Consider the solution to be ideal.

Contoh 12
What is the composition, expressed as mole fractions, of the vapor in equilibrium with the benzenetoluene solution of Example 12.11?

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Distilasi Fraksional
The vapor here

is richer in the more volatile component than the original liquid here

so the liquid that condenses here will also be richer in the more volatile component.

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Contoh 13
Figure 12.16 (below) shows two different aqueous solutions placed in the same enclosure. After a time, the solution level has risen in container A and dropped in container B. Explain how and why this happens.

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Penurunan Tekanan Uap oleh Solut Non Volatil

the vapor pressure from the pure solvent.

Raoults Law: the vapor pressure from a solution (nonvolatile solute) is lower than

Result: the boiling point of the solution increases by Tb.

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Penurunan Titik Beku dan Kenaikan Titik Didih

Tf = Kf m Tb = Kb m

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Contoh 14
What is the freezing point of an aqueous sucrose solution that has 25.0 g C12H22O11 per 100.0 g H2O?

Contoh 15
Sorbitol is a sweet substance found in fruits and berries and sometimes used as a sugar substitute. An aqueous solution containing 1.00 g sorbitol in 100.0 g water is found to have a freezing point of 0.102 C. Elemental analysis indicates that sorbitol consists of 39.56% C, 7.75% H, and 52.70% O by mass. What are the (a) molar mass and (b) molecular formula of sorbitol?

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Tekanan Osmotik
Suatu membran semipermiabel memiliki pori mikroskopis yang dapat dilalui molekul solven yang kecil tetapi tidak dapat dilalu molekul solut yang lebih besar. selama osmosis, terjadi aliran molekul solven malalui membran semipermiabel, dari tempat dengan konsentrasi rendah menuju tempat dengan konsentrasi lebih tinggi. Tekanan yang diperlukan untuk mencegah terjadinya osmosis dinamakan osmotic pressure () (tekanan osmotik) dari suatu larutan.

= (nRT/V) = (n/V)RT = M RT

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Osmosis dan Tekanan Osmotik

The solution increases in volume until

the height of solution exerts the osmotic pressure () of the solution.

Net flow of water from the outside (pure H2O) to the solution.

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Contoh 16
An aqueous solution is prepared by dissolving 1.50 g of hemocyanin, a protein obtained from crabs, in 0.250 L of water. The solution has an osmotic pressure of 0.00342 atm at 277 K. (a) What is the molar mass of hemocyanin? (b) What should the freezing point of the solution be?

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Aplikasi Osmosis
Pasien harus diberikan cairan intravena yang isotonik memiliki tekanan osmotik yang sama dengan darah.
External solution is hypertonic; produces osmotic pressure > int. Net flow of water out of the cell. Red blood cell in isotonic solution remains the same size. External solution is hypotonic; produces osmotic pressure < int. Net flow of water into the cell.

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Aplikasi Osmosis
Reverse osmosis (RO): kebalikan dari arah aliran solven melalui membran semipermiabel. Tekanan yang lebih besar dari tekanan osmotik dikenakan kepada larutan. RO digunakan untuk pemurnian air (pembuatan air tawar dari air laut).

Pressure greater than is applied here

water flows from the more concentrated solution, through the membrane.

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Larutan Elektrolit
Jika elektrolit terdisosiasi, jumlah partikel solut biasanya lebih besar dari jumlah partikel senyawa yang terlarut. Satu mol NaCl terlarut di dalam air menghasilkan lebih dari satu mol partikel. vant Hoff factor (i) digunakan untuk modifikasi persamaan sifat koligatif untuk senyawa elektrolit sebagai berikut: Tf = i (Kf) m Tb = i Kb m = i M RT Untuk solut non elektrolit, i = 1. Untuk Elektrolit, i sama dengan jumlah ion yang diperoleh dari senyawa jika senyawa tersebut terdisosiasi dalam larutan.

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At very low concentrations, the theoretical values of i are reached.

At higher concentrations, the values of i are significantly lower than the theoretical values; ion pairs form in solution.

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Contoh 17
Without doing detailed calculations, place the following solutions in order of decreasing osmotic pressure: 0.01 M C12H22O11(aq) at 25 C 0.01 M CH3CH2COOH(aq) at 37 C 0.01 m KNO3(aq) at 25 C a solution of 1.00 g polystyrene (molar mass: 3.5 105 g/mol) in 100 mL of benzene at 25 C

(a) (b) (c) (d)

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Koloid
Dalam larutan, partikel terdispersi merupakan molekul, atom, atau ion (berukuran 0,1 nm). Partikel solut tidak mengendap di dalam larutan. Dalam suspensi (Misal: pasir dalam air) partikel terdispersi berukuran cukup besar dan akan mengendap dari suspensinya. dalam koloid, partikel terdispersi berukuran 11000 nm. Meskipun lebih besar dari molekul/ato.ion, partikel koloid cukup kecil untuk tetap terdispersi di dalam cairan.

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Why are there no gasin-gas colloids?

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Efek Tyndall
Light scattered by the (larger) colloidal particles of Fe2O3 makes the beam visible.

The dissolved Fe3+ ions are not large enough to scatter light; the beam is virtually invisible.

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Suspensi dan Koloid

Suspended SiO2 (sand) settles very quickly.

Each colloidal particle of SiO2 (Ludox) attains a () charge, which repels other colloidal particles.

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Pembentukan dan Koagulasi Koloid

When a strong electrolyte is added to colloidal iron oxide, the charge on the surface of each particle is partially neutralized

and the colloidal particles coalesce into a suspension that quickly settles.

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Latihan Kumulatif
A 375-mL sample of hexane vapor in equilibrium with liquid hexane C6H14 (d = 0.6548 g/mL), at 25.0 C is dissolved in 50.0 mL of liquid cyclohexane, C6H12, at 25.0 C (d = 0.7739 g/mL, vp = 97.58 Torr). Use information found elsewhere in the text (such as Example 11.3) to calculate the total vapor pressure above the solution at 25.0 C. How reliable is this calculation?

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