Employees are entitled to annual and personal leave that is accrued as they work. Whether the leave appears in the Pro-rata or Entitlement balance will depend on how the leave table code has been set up. See Setups, Payroll, Leave Tables, Enquire.

If a leave accruals code has been set up to calculate leave using the hourly calculation method (Calculate by Hours) and the Entitlement is an amount per 1 hour worked (Entitlement Period) then the accrual balance is generally going to all show in the Entitlement balance. There may be a small amount that shows in the Pro rata column if the employee works a total of whole hours.
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This method will often show two lines on the Leave History report. The first line shows the accrual amount and the hours worked, and the second line shows a positive and negative amount moving the entitlement to this column.
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However, if your accrual is set up using the Date method (Calculate by Date) and the Entitlement is say 4 weeks per 1 year Entitlement Period then the accrual will appear in the Pro-rata balance until the year has been completed. After the year the balance will move into the Entitlement balance.

Any leave taken always comes off the Entitlement balance and so sometimes this might show as a negative value. But it is the total of the Entitlement and Pro-rata balances that the employee is entitled to for annual and personal leave. Therefore, it is always sensible to show the Combined leave balance on the Pay advice to avoid any confusion for these balances. See Display leave balances on pay advices.

Long Service leave is a bit different from the other leave types. There is normally a Contingent period entered say 7 years. Employees are not entitled to the Contingent balance accrued. The accrual would sit in the Contingent balance until the end of this period then it would move to the Pro-rata balance which is often payable on termination. Once the balance has moved to the Entitlement period then the employee is able to take this leave.